Sulfurized estolides and methods of making and using the same

ABSTRACT

Provided herein are compounds of the formula: 
     
       
         
         
             
             
         
       
     
     in which n is an integer equal to or greater than 1; m is an integer equal to or greater than 1; R 2  is selected from hydrogen and optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched; and R 1 , R 3 , and R 4 , independently for each occurrence, are selected from optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched, wherein at least one of R 1 , R 2 , R 3 , or R 4  is sulfurized or epoxidized. Also provided are compositions containing the compounds and methods of making both the compounds and compositions thereof.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit under 35 U.S.C. §119(e) of U.S.Provisional Patent Application No. 61/498,499, filed Jun. 17, 2011, U.S.Provisional Patent Application No. 61/569,046, filed Dec. 9, 2011, andU.S. Provisional Patent Application No. 61/583,139, filed Jan. 4, 2012,which are incorporated herein by reference in their entireties for allpurposes.

FIELD

The present disclosure relates to epoxidized estolides, sulfurizedestolides, and methods of making the same. The estolides describedherein may be suitable for use as lubricants, lubricant additives, andplasticizers.

BACKGROUND

Lubricant compositions may be modified to alter and/or improve theproperties of the lubricant. For example, anti-wear additives may beused in lubricating compositions to provide reduced friction and/orextreme pressure protection. Similarly, plastics and plasticizedcompositions can be specifically formulated to meet desiredcharacteristics. For example, plasticizers may be added to polymericcompositions to impart flexibility and pliability.

SUMMARY

Described herein are estolide compounds, estolide-containingcompositions, and methods of making the same. In certain embodiments,such compounds and/or compositions may be useful as lubricants andadditives.

In certain embodiments, the estolides comprise at least one compound ofFormula I:

-   -   wherein    -   W¹, W², W³, W⁴, W⁵, W⁶, and W⁷, independently for each        occurrence, are selected from —CH₂—, —CH═CH—, —CHR₅—, and

-   -   R₅ is selected from a halogen and —S_(v)R₆, wherein v is an        integer selected from 1 to 8 and R₆ is selected from hydrogen        and an estolide residue;    -   T is selected from O and S;    -   z is an integer selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,        11, 12, 13, 14, and 15;    -   p is an integer selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,        11, 12, 13, 14, and 15;    -   q is an integer selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,        11, 12, 13, 14, and 15;    -   x is, independently for each occurrence, an integer selected        from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,        17, 18, 19, and 20;    -   y is, independently for each occurrence, an integer selected        from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,        17, 18, 19, and 20;    -   n is equal to or greater than 0; and    -   R₂ is selected from hydrogen and optionally substituted alkyl        that is saturated or unsaturated, and branched or unbranched,    -   wherein each fatty acid chain residue of said at least one        compound is independently optionally substituted, and    -   wherein at least one of W¹, W², W³, W⁴, W⁵, W⁶, and W⁷ is —CHR₅—        or

In certain embodiments, the estolides comprise at least one compound ofFormula II:

-   -   wherein    -   m is an integer equal to or greater than 1;    -   n is an integer equal to or greater than 0;    -   R₁, independently for each occurrence, is an optionally        substituted alkyl that is saturated or unsaturated, branched or        unbranched;    -   R₂ is selected from hydrogen and optionally substituted alkyl        that is saturated or unsaturated, and branched or unbranched;        and    -   R₃ and R₄, independently for each occurrence, are selected from        optionally substituted alkyl that is saturated or unsaturated,        and branched or unbranched,    -   wherein at least one of R₁, R₂, R₃, or R₄ is sulfurized or        epoxidized.

In certain embodiments, the estolides comprise at least one estolidecompound of Formula III:

-   -   wherein    -   T is selected from O and S;    -   z is an integer selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,        11, 12, 13, 14, and 15;    -   q is an integer selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,        11, 12, 13, 14, and 15;    -   x is, independently for each occurrence, an integer selected        from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,        17, 18, 19, and 20;    -   y is, independently for each occurrence, an integer selected        from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,        17, 18, 19, and 20;    -   n is equal to or greater than 0; and    -   R₂ is selected from hydrogen and optionally substituted alkyl        that is saturated or unsaturated, and branched or unbranched,    -   wherein each fatty acid chain residue of said at least one        compound is independently optionally substituted.

A process of producing a lubricant composition is also described. Incertain embodiments, the process comprises:

-   -   selecting at least one estolide compound; and    -   sulfurizing at least a portion of the at least one estolide        compound.

A process of producing a plasticized composition is also described. Incertain embodiments, the process comprises:

-   -   selecting at least one estolide compound;    -   epoxidizing at least a portion of the at least one estolide        compound; and    -   contacting at least one polymeric material with the epoxidized        estolide compound to provide a plasticized composition.

DETAILED DESCRIPTION

The use of lubricant and plasticizer compounds, and/or compositions mayresult in the dispersion of such fluids, compounds, and/or compositionsin the environment. Petroleum base oils used in common lubricant andplasticized compositions, as well as additives, are typicallynon-biodegradable and can be toxic. The present disclosure provides forthe preparation and use of lubricant and plasticized compositionscomprising partially or fully bio-degradable compounds, including baseoils comprising one or more estolides.

In certain embodiments, the compounds and/or compositions comprising oneor more estolides are partially or fully biodegradable and thereby posediminished risk to the environment. In certain embodiments, thecompounds and/or compositions meet guidelines set for by theOrganization for Economic Cooperation and Development (OECD) fordegradation and accumulation testing. The OECD has indicated thatseveral tests may be used to determine the “ready biodegradability” oforganic chemicals. Aerobic ready biodegradability by OECD 301D measuresthe mineralization of the test sample to CO₂ in closed aerobicmicrocosms that simulate an aerobic aquatic environment, withmicroorganisms seeded from a waste-water treatment plant. OECD 301D isconsidered representative of most aerobic environments that are likelyto receive waste materials. Aerobic “ultimate biodegradability” can bedetermined by OECD 302D. Under OECD 302D, microorganisms arepre-acclimated to biodegradation of the test material during apre-incubation period, then incubated in sealed vessels with relativelyhigh concentrations of microorganisms and enriched mineral salts medium.OECD 302D ultimately determines whether the test materials arecompletely biodegradable, albeit under less stringent conditions than“ready biodegradability” assays.

As used in the present specification, the following words, phrases andsymbols are generally intended to have the meanings as set forth below,except to the extent that the context in which they are used indicatesotherwise. The following abbreviations and terms have the indicatedmeanings throughout:

A dash (“-”) that is not between two letters or symbols is used toindicate a point of attachment for a substituent. For example, —C(O)NH₂is attached through the carbon atom.

“Alkoxy” by itself or as part of another substituent refers to a radical—OR³¹ where R³¹ is alkyl, cycloalkyl, cycloalkylalkyl, aryl, orarylalkyl, which can be substituted, as defined herein. In someembodiments, alkoxy groups have from 1 to 8 carbon atoms. In someembodiments, alkoxy groups have 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms.Examples of alkoxy groups include, but are not limited to, methoxy,ethoxy, propoxy, butoxy, cyclohexyloxy, and the like.

“Alkyl” by itself or as part of another substituent refers to asaturated or unsaturated, branched, or straight-chain monovalenthydrocarbon radical derived by the removal of one hydrogen atom from asingle carbon atom of a parent alkane, alkene, or alkyne. Examples ofalkyl groups include, but are not limited to, methyl; ethyls such asethanyl, ethenyl, and ethynyl; propyls such as propan-1-yl, propan-2-yl,prop-1-en-1-yl, prop-1-en-2-yl, prop-2-en-1-yl (allyl), prop-1-yn-1-yl,prop-2-yn-1-yl, etc.; butyls such as butan-1-yl, butan-2-yl,2-methyl-propan-1-yl, 2-methyl-propan-2-yl, but-1-en-1-yl,but-1-en-2-yl, 2-methyl-prop-1-en-1-yl, but-2-en-1-yl, but-2-en-2-yl,buta-1,3-dien-1-yl, buta-1,3-dien-2-yl, but-1-yn-1-yl, but-1-yn-3-yl,but-3-yn-1-yl, etc.; and the like.

Unless otherwise indicated, the term “alkyl” is specifically intended toinclude groups having any degree or level of saturation, i.e., groupshaving exclusively single carbon-carbon bonds, groups having one or moredouble carbon-carbon bonds, groups having one or more triplecarbon-carbon bonds, and groups having mixtures of single, double, andtriple carbon-carbon bonds. Where a specific level of saturation isintended, the terms “alkanyl,” “alkenyl,” and “alkynyl” are used. Incertain embodiments, an alkyl group comprises from 1 to 40 carbon atoms,in certain embodiments, from 1 to 22 or 1 to 18 carbon atoms, in certainembodiments, from 1 to 16 or 1 to 8 carbon atoms, and in certainembodiments from 1 to 6 or 1 to 3 carbon atoms. In certain embodiments,an alkyl group comprises from 8 to 22 carbon atoms, in certainembodiments, from 8 to 18 or 8 to 16. In some embodiments, the alkylgroup comprises from 3 to 20 or 7 to 17 carbons. In some embodiments,the alkyl group comprises 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,15, 16, 17, 18, 19, 20, 21, or 22 carbon atoms.

“Aryl” by itself or as part of another substituent refers to amonovalent aromatic hydrocarbon radical derived by the removal of onehydrogen atom from a single carbon atom of a parent aromatic ringsystem. Aryl encompasses 5- and 6-membered carbocyclic aromatic rings,for example, benzene; bicyclic ring systems wherein at least one ring iscarbocyclic and aromatic, for example, naphthalene, indane, andtetralin; and tricyclic ring systems wherein at least one ring iscarbocyclic and aromatic, for example, fluorene. Aryl encompassesmultiple ring systems having at least one carbocyclic aromatic ringfused to at least one carbocyclic aromatic ring, cycloalkyl ring, orheterocycloalkyl ring. For example, aryl includes 5- and 6-memberedcarbocyclic aromatic rings fused to a 5- to 7-membered non-aromaticheterocycloalkyl ring containing one or more heteroatoms chosen from N,O, and S. For such fused, bicyclic ring systems wherein only one of therings is a carbocyclic aromatic ring, the point of attachment may be atthe carbocyclic aromatic ring or the heterocycloalkyl ring. Examples ofaryl groups include, but are not limited to, groups derived fromaceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene,benzene, chrysene, coronene, fluoranthene, fluorene, hexacene,hexaphene, hexylene, as-indacene, s-indacene, indane, indene,naphthalene, octacene, octaphene, octalene, ovalene, penta-2,4-diene,pentacene, pentalene, pentaphene, perylene, phenalene, phenanthrene,picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene,trinaphthalene, and the like. In certain embodiments, an aryl group cancomprise from 5 to 20 carbon atoms, and in certain embodiments, from 5to 12 carbon atoms. In certain embodiments, an aryl group can comprise5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbonatoms. Aryl, however, does not encompass or overlap in any way withheteroaryl, separately defined herein. Hence, a multiple ring system inwhich one or more carbocyclic aromatic rings is fused to aheterocycloalkyl aromatic ring, is heteroaryl, not aryl, as definedherein.

“Arylalkyl” by itself or as part of another substituent refers to anacyclic alkyl radical in which one of the hydrogen atoms bonded to acarbon atom, typically a terminal or sp³ carbon atom, is replaced withan aryl group. Examples of arylalkyl groups include, but are not limitedto, benzyl, 2-phenylethan-1-yl, 2-phenylethen-1-yl, naphthylmethyl,2-naphthylethan-1-yl, 2-naphthylethen-1-yl, naphthobenzyl,2-naphthophenylethan-1-yl, and the like. Where specific alkyl moietiesare intended, the nomenclature arylalkanyl, arylalkenyl, or arylalkynylis used. In certain embodiments, an arylalkyl group is C₇₋₃₀ arylalkyl,e.g., the alkanyl, alkenyl, or alkynyl moiety of the arylalkyl group isC₁₋₁₀ and the aryl moiety is C₆₋₂₀, and in certain embodiments, anarylalkyl group is C₇₋₂₀ arylalkyl, e.g., the alkanyl, alkenyl, oralkynyl moiety of the arylalkyl group is C₁₋₈ and the aryl moiety isC₆₋₁₂.

Estolide “base oil” and “base stock”, unless otherwise indicated, referto any composition comprising one or more estolide compounds. It shouldbe understood that an estolide “base oil” or “base stock” is not limitedto compositions for a particular use, and may generally refer tocompositions comprising one or more estolides, including mixtures ofestolides. Estolide base oils and base stocks can also include compoundsother than estolides.

“Compounds” refers to compounds encompassed by structural Formula I, II,and III herein and includes any specific compounds within the formulawhose structure is disclosed herein. Compounds may be identified eitherby their chemical structure and/or chemical name. When the chemicalstructure and chemical name conflict, the chemical structure isdeterminative of the identity of the compound. The compounds describedherein may contain one or more chiral centers and/or double bonds andtherefore may exist as stereoisomers such as double-bond isomers (i.e.,geometric isomers), enantiomers, or diastereomers. Accordingly, anychemical structures within the scope of the specification depicted, inwhole or in part, with a relative configuration encompass all possibleenantiomers and stereoisomers of the illustrated compounds including thestereoisomerically pure form (e.g., geometrically pure, enantiomericallypure, or diastereomerically pure) and enantiomeric and stereoisomericmixtures. Enantiomeric and stereoisomeric mixtures may be resolved intotheir component enantiomers or stereoisomers using separation techniquesor chiral synthesis techniques well known to the skilled artisan.

For the purposes of the present disclosure, “chiral compounds” arecompounds having at least one center of chirality (i.e. at least oneasymmetric atom, in particular at least one asymmetric C atom), havingan axis of chirality, a plane of chirality or a screw structure.“Achiral compounds” are compounds which are not chiral.

Compounds of Formula I, II, and III include, but are not limited to,optical isomers of compounds of Formula I, II, and III, racematesthereof, and other mixtures thereof. In such embodiments, the singleenantiomers or diastereomers, i.e., optically active forms, can beobtained by asymmetric synthesis or by resolution of the racemates.Resolution of the racemates may be accomplished by, for example,chromatography, using, for example a chiral high-pressure liquidchromatography (HPLC) column. However, unless otherwise stated, itshould be assumed that Formula I, II, and III cover all asymmetricvariants of the compounds described herein, including isomers,racemates, enantiomers, diastereomers, and other mixtures thereof. Inaddition, compounds of Formula I, II and III include Z- and E-forms(e.g., cis- and trans-forms) of compounds with double bonds. Thecompounds of Formula I, II, and III may also exist in several tautomericforms including the enol form, the keto form, and mixtures thereof.Accordingly, the chemical structures depicted herein encompass allpossible tautomeric forms of the illustrated compounds.

“Cycloalkyl” by itself or as part of another substituent refers to asaturated or unsaturated cyclic alkyl radical. Where a specific level ofsaturation is intended, the nomenclature “cycloalkanyl” or“cycloalkenyl” is used. Examples of cycloalkyl groups include, but arenot limited to, groups derived from cyclopropane, cyclobutane,cyclopentane, cyclohexane, and the like. In certain embodiments, acycloalkyl group is C₃₋₁₅ cycloalkyl, and in certain embodiments, C₃₋₁₂cycloalkyl or C₅₋₁₂ cycloalkyl. In certain embodiments, a cycloalkylgroup is a C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, or C₁₅cycloalkyl.

“Cycloalkylalkyl” by itself or as part of another substituent refers toan acyclic alkyl radical in which one of the hydrogen atoms bonded to acarbon atom, typically a terminal or sp³ carbon atom, is replaced with acycloalkyl group. Where specific alkyl moieties are intended, thenomenclature cycloalkylalkanyl, cycloalkylalkenyl, or cycloalkylalkynylis used. In certain embodiments, a cycloalkylalkyl group is C₇₋₃₀cycloalkylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of thecycloalkylalkyl group is C₁₋₁₀ and the cycloalkyl moiety is C₆₋₂₀, andin certain embodiments, a cycloalkylalkyl group is C₇₋₂₀cycloalkylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of thecycloalkylalkyl group is C₁₋₈ and the cycloalkyl moiety is C₄₋₂₀ orC₆₋₁₂.

“Halogen” refers to a fluoro, chloro, bromo, or iodo group.

“Heteroaryl” by itself or as part of another substituent refers to amonovalent heteroaromatic radical derived by the removal of one hydrogenatom from a single atom of a parent heteroaromatic ring system.Heteroaryl encompasses multiple ring systems having at least onearomatic ring fused to at least one other ring, which can be aromatic ornon-aromatic in which at least one ring atom is a heteroatom. Heteroarylencompasses 5- to 12-membered aromatic, such as 5- to 7-membered,monocyclic rings containing one or more, for example, from 1 to 4, or incertain embodiments, from 1 to 3, heteroatoms chosen from N, O, and S,with the remaining ring atoms being carbon; and bicyclicheterocycloalkyl rings containing one or more, for example, from 1 to 4,or in certain embodiments, from 1 to 3, heteroatoms chosen from N, O,and S, with the remaining ring atoms being carbon and wherein at leastone heteroatom is present in an aromatic ring. For example, heteroarylincludes a 5- to 7-membered heterocycloalkyl, aromatic ring fused to a5- to 7-membered cycloalkyl ring. For such fused, bicyclic heteroarylring systems wherein only one of the rings contains one or moreheteroatoms, the point of attachment may be at the heteroaromatic ringor the cycloalkyl ring. In certain embodiments, when the total number ofN, S, and O atoms in the heteroaryl group exceeds one, the heteroatomsare not adjacent to one another. In certain embodiments, the totalnumber of N, S, and O atoms in the heteroaryl group is not more thantwo. In certain embodiments, the total number of N, S, and O atoms inthe aromatic heterocycle is not more than one. Heteroaryl does notencompass or overlap with aryl as defined herein.

Examples of heteroaryl groups include, but are not limited to, groupsderived from acridine, arsindole, carbazole, β-carboline, chromane,chromene, cinnoline, furan, imidazole, indazole, indole, indoline,indolizine, isobenzofuran, isochromene, isoindole, isoindoline,isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole,oxazole, perimidine, phenanthridine, phenanthroline, phenazine,phthalazine, pteridine, purine, pyran, pyrazine, pyrazole, pyridazine,pyridine, pyrimidine, pyrrole, pyrrolizine, quinazoline, quinoline,quinolizine, quinoxaline, tetrazole, thiadiazole, thiazole, thiophene,triazole, xanthene, and the like. In certain embodiments, a heteroarylgroup is from 5- to 20-membered heteroaryl, and in certain embodimentsfrom 5- to 12-membered heteroaryl or from 5- to 10-membered heteroaryl.In certain embodiments, a heteroaryl group is a 5-, 6-, 7-, 8-, 9-, 10-,11-, 12-, 13-, 14-, 15-, 16-, 17-, 18-, 19-, or 20-membered heteroaryl.In certain embodiments heteroaryl groups are those derived fromthiophene, pyrrole, benzothiophene, benzofuran, indole, pyridine,quinoline, imidazole, oxazole, and pyrazine.

“Heteroarylalkyl” by itself or as part of another substituent refers toan acyclic alkyl radical in which one of the hydrogen atoms bonded to acarbon atom, typically a terminal or sp³ carbon atom, is replaced with aheteroaryl group. Where specific alkyl moieties are intended, thenomenclature heteroarylalkanyl, heteroarylalkenyl, or heteroarylalkynylis used. In certain embodiments, a heteroarylalkyl group is a 6- to30-membered heteroarylalkyl, e.g., the alkanyl, alkenyl, or alkynylmoiety of the heteroarylalkyl is 1- to 10-membered and the heteroarylmoiety is a 5- to 20-membered heteroaryl, and in certain embodiments, 6-to 20-membered heteroarylalkyl, e.g., the alkanyl, alkenyl, or alkynylmoiety of the heteroarylalkyl is 1- to 8-membered and the heteroarylmoiety is a 5- to 12-membered heteroaryl.

“Heterocycloalkyl” by itself or as part of another substituent refers toa partially saturated or unsaturated cyclic alkyl radical in which oneor more carbon atoms (and any associated hydrogen atoms) areindependently replaced with the same or different heteroatom. Examplesof heteroatoms to replace the carbon atom(s) include, but are notlimited to, N, P, O, S, Si, etc. Where a specific level of saturation isintended, the nomenclature “heterocycloalkanyl” or “heterocycloalkenyl”is used. Examples of heterocycloalkyl groups include, but are notlimited to, groups derived from epoxides, azirines, thiiranes,imidazolidine, morpholine, piperazine, piperidine, pyrazolidine,pyrrolidine, quinuclidine, and the like.

“Heterocycloalkylalkyl” by itself or as part of another substituentrefers to an acyclic alkyl radical in which one of the hydrogen atomsbonded to a carbon atom, typically a terminal or sp³ carbon atom, isreplaced with a heterocycloalkyl group. Where specific alkyl moietiesare intended, the nomenclature heterocycloalkylalkanyl,heterocycloalkylalkenyl, or heterocycloalkylalkynyl is used. In certainembodiments, a heterocycloalkylalkyl group is a 6- to 30-memberedheterocycloalkylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety ofthe heterocycloalkylalkyl is 1- to 10-membered and the heterocycloalkylmoiety is a 5- to 20-membered heterocycloalkyl, and in certainembodiments, 6- to 20-membered heterocycloalkylalkyl, e.g., the alkanyl,alkenyl, or alkynyl moiety of the heterocycloalkylalkyl is 1- to8-membered and the heterocycloalkyl moiety is a 5- to 12-memberedheterocycloalkyl.

“Mixture” refers to a collection of molecules or chemical substances.Each component in a mixture can be independently varied. A mixture maycontain, or consist essentially of, two or more substances intermingledwith or without a constant percentage composition, wherein eachcomponent may or may not retain its essential original properties, andwhere molecular phase mixing may or may not occur. In mixtures, thecomponents making up the mixture may or may not remain distinguishablefrom each other by virtue of their chemical structure.

“Parent aromatic ring system” refers to an unsaturated cyclic orpolycyclic ring system having a conjugated π (pi) electron system.Included within the definition of “parent aromatic ring system” arefused ring systems in which one or more of the rings are aromatic andone or more of the rings are saturated or unsaturated, such as, forexample, fluorene, indane, indene, phenalene, etc. Examples of parentaromatic ring systems include, but are not limited to, aceanthrylene,acenaphthylene, acephenanthrylene, anthracene, azulene, benzene,chrysene, coronene, fluoranthene, fluorene, hexacene, hexaphene,hexylene, as-indacene, s-indacene, indane, indene, naphthalene,octacene, octaphene, octalene, ovalene, penta-2,4-diene, pentacene,pentalene, pentaphene, perylene, phenalene, phenanthrene, picene,pleiadene, pyrene, pyranthrene, rubicene, triphenylene, trinaphthalene,and the like.

“Parent heteroaromatic ring system” refers to a parent aromatic ringsystem in which one or more carbon atoms (and any associated hydrogenatoms) are independently replaced with the same or different heteroatom.Examples of heteroatoms to replace the carbon atoms include, but are notlimited to, N, P, O, S, Si, etc. Specifically included within thedefinition of “parent heteroaromatic ring systems” are fused ringsystems in which one or more of the rings are aromatic and one or moreof the rings are saturated or unsaturated, such as, for example,arsindole, benzodioxan, benzofuran, chromane, chromene, indole,indoline, xanthene, etc. Examples of parent heteroaromatic ring systemsinclude, but are not limited to, arsindole, carbazole, β-carboline,chromane, chromene, cinnoline, furan, imidazole, indazole, indole,indoline, indolizine, isobenzofuran, isochromene, isoindole,isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine,oxadiazole, oxazole, perimidine, phenanthridine, phenanthroline,phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazole,pyridazine, pyridine, pyrimidine, pyrrole, pyrrolizine, quinazoline,quinoline, quinolizine, quinoxaline, tetrazole, thiadiazole, thiazole,thiophene, triazole, xanthene, and the like.

“Substituted” refers to a group in which one or more hydrogen atoms areindependently replaced with the same or different substituent(s).Examples of substituents include, but are not limited to, —R⁶⁴, —R⁶⁰,—O⁻, —OH, ═O, —OR⁶⁰, —SR⁶⁰, —S⁻, ═S, —NR⁶⁰R⁶¹, ═NR⁶⁰, —CN, —CF₃, —OCN,—SCN, —NO, —NO₂, ═N₂, —N₃, —S(O)₂O⁻, —S(O)₂OH, —S(O)₂R⁶⁰, —OS(O₂)O⁻,—OS(O)₂R⁶⁰, —P(O)(O⁻)₂, —P(O)(OR⁶⁰)(O⁻), —OP(O)(OR⁶⁰)(OR⁶¹), —C(O)R⁶⁰,—C(S)R⁶⁰, —C(O)OR⁶⁰, —C(O)NR⁶⁰R⁶¹, —C(O)O⁻, —C(S)OR⁶⁰, —NR⁶²C(O)NR⁶⁰R⁶¹,—NR⁶²C(S)NR⁶⁰R⁶¹, —NR⁶²C(NR⁶³NR⁶⁰R⁶¹, —C(NR⁶²)NR⁶OR⁶¹, —S(O)₂, NR⁶⁰R⁶¹,—NR⁶³S(O)₂R⁶⁰, —NR⁶³C(O)R⁶⁰, and —S(O)R⁶⁰;

wherein each —R⁶⁴ is independently a halogen; each R⁶⁰ and R⁶¹ areindependently alkyl, substituted alkyl, alkoxy, substituted alkoxy,cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, arylalkyl, substituted arylalkyl, heteroarylalkyl, orsubstituted heteroarylalkyl, or R⁶⁰ and R⁶¹ together with the nitrogenatom to which they are bonded form a heterocycloalkyl, substitutedheterocycloalkyl, heteroaryl, or substituted heteroaryl ring, and R⁶²and R⁶³ are independently alkyl, substituted alkyl, aryl, substitutedaryl, arylalkyl, substituted arylalkyl, cycloalkyl, substitutedcycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, heteroaryl,substituted heteroaryl, heteroarylalkyl, or substituted heteroarylalkyl,or R⁶² and R⁶³ together with the atom to which they are bonded form oneor more heterocycloalkyl, substituted heterocycloalkyl, heteroaryl, orsubstituted heteroaryl rings;

wherein the “substituted” substituents, as defined above for R⁶⁰, R⁶¹,R⁶², and R⁶³, are substituted with one or more, such as one, two, orthree, groups independently selected from alkyl, -alkyl-OH,—O-haloalkyl, -alkyl-NH₂, alkoxy, cycloalkyl, cycloalkylalkyl,heterocycloalkyl, heterocycloalkylalkyl, aryl, heteroaryl, arylalkyl,heteroarylalkyl, —O⁻, —OH, ═O, —O-alkyl, —O-aryl, —O-heteroarylalkyl,—O-cycloalkyl, —O-heterocycloalkyl, —SH, —S⁻, ═S, —S-alkyl, —S-aryl,—S-heteroarylalkyl, —S-cycloalkyl, —S-heterocycloalkyl, —NH₂, ═NH, —CN,—CF₃, —OCN, —SCN, —NO, —NO₂, ═N₂, —N₃, —S(O)₂O⁻, —S(O)₂, —S(O)₂OH,—OS(O₂)O⁻, —SO₂(alkyl), —SO₂(phenyl), —SO₂(haloalkyl), —SO₂NH₂,—SO₂NH(alkyl), —SO₂NH(phenyl), —P(O)(O)₂, —P(O)(O-alkyl)(O⁻),—OP(O)(O-alkyl)(O-alkyl), —CO₂H, —C(O)O(alkyl), —CON(alkyl)(alkyl),—CONH(alkyl), —CONH₂, —C(O)(alkyl), —C(O)(phenyl), —C(O)(haloalkyl),—OC(O)(alkyl), —N(alkyl)(alkyl), —NH(alkyl), —N(alkyl)(alkylphenyl),—NH(alkylphenyl), —NHC(O)(alkyl), —NHC(O)(phenyl), —N(alkyl)C(O)(alkyl),and —N(alkyl)C(O)(phenyl).

As used in this specification and the appended claims, the articles “a,”“an,” and “the” include plural referents unless expressly andunequivocally limited to one referent.

The term “fatty acid” refers to any natural or synthetic carboxylic acidcomprising an alkyl chain that may be saturated, monounsaturated, orpolyunsaturated, and may have straight or branched chains. The fattyacid may also be substituted. “Fatty acid,” as used herein, includesshort chain alkyl carboxylic acid including, for example, acetic acid,propionic acid, etc.

All numerical ranges herein include all numerical values and ranges ofall numerical values within the recited range of numerical values.

The present disclosure relates to estolide compounds, compositions andmethods of making the same. In certain embodiments, the presentdisclosure also relates to estolide compounds, compositions comprisingestolide compounds, the synthesis of such compounds, and the formulationof such compositions. In certain embodiments, the present disclosurerelates to biosynthetic estolides having desired viscometric properties,while retaining or even improving other properties such as oxidativestability and pour point. In certain embodiments, new methods ofpreparing estolide compounds exhibiting such properties are provided.The present disclosure also relates to compositions comprising certainestolide compounds exhibiting such properties.

In certain embodiments, the estolides comprise at least one compound ofFormula I:

-   -   wherein    -   W¹, W², W³, W⁴, W⁵, W⁶, and W⁷, independently for each        occurrence, are selected from —CH₂—, —CH═CH—, —CHR₅—, and

-   -   R₅ is selected from a halogen and —S_(v)R₆, wherein v is an        integer selected from 1 to 8 and R₆ is selected from hydrogen        and an estolide residue;    -   T is selected from O and S;    -   z is an integer selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,        11, 12, 13, 14, and 15;    -   p is an integer selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,        11, 12, 13, 14, and 15;    -   q is an integer selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,        11, 12, 13, 14, and 15;    -   x is, independently for each occurrence, an integer selected        from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,        17, 18, 19, and 20;    -   y is, independently for each occurrence, an integer selected        from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,        17, 18, 19, and 20;    -   n is equal to or greater than 0; and    -   R₂ is selected from hydrogen and optionally substituted alkyl        that is saturated or unsaturated, and branched or unbranched,    -   wherein each fatty acid chain residue of said at least one        compound is independently optionally substituted, and    -   wherein at least one of W¹, W², W³, W⁴, W⁵, W⁶, and W⁷ is —CHR₅—        or

In certain embodiments, the estolides comprise at least one compound ofFormula II:

-   -   wherein    -   m is an integer equal to or greater than 1;    -   n is an integer equal to or greater than 0;    -   R₁, independently for each occurrence, is an optionally        substituted alkyl that is saturated or unsaturated, branched or        unbranched;    -   R₂ is selected from hydrogen and optionally substituted alkyl        that is saturated or unsaturated, and branched or unbranched;        and    -   R₃ and R₄, independently for each occurrence, are selected from        optionally substituted alkyl that is saturated or unsaturated,        and branched or unbranched,    -   wherein at least one of R₁, R₂, R₃, or R₄ is epoxidized or        sulfurized.

In certain embodiments, the estolides comprise at least one compound ofFormula III:

-   -   wherein    -   T is selected from O and S;    -   z is an integer selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,        11, 12, 13, 14, and 15;    -   q is an integer selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,        11, 12, 13, 14, and 15;    -   x is, independently for each occurrence, an integer selected        from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,        17, 18, 19, and 20;    -   y is, independently for each occurrence, an integer selected        from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,        17, 18, 19, and 20;    -   n is equal to or greater than 0; and    -   R₂ is selected from hydrogen and optionally substituted alkyl        that is saturated or unsaturated, and branched or unbranched,    -   wherein each fatty acid chain residue of said at least one        compound is independently optionally substituted.

The terms “chain” or “fatty acid chain” or “fatty acid chain residue,”as used with respect to the estolide compounds of Formula I, II, andIII, refer to one or more of the fatty acid residues incorporated inestolide compounds, e.g., R₃ or R₄ of Formula II, the structuresrepresented by

and CH₃(CH₂)_(y)CH(CH₂)—C(O)O— in Formula III, or the structuresrepresented by CH₃(W¹)_(q)CH₂(W²)_(p)CH₂(W³)_(z)—C(O)—O—,CH₃(W⁴)_(y)CH₂(W⁵)_(x)—C(O)—O—, and CH₃(W⁶)_(y)CH₂(W⁷)_(x)—C(O)—O— inFormula I.

The R₁ of Formula II is an example of what may be referred to as a “cap”or “capping material,” as it “caps” the top of the estolide. Forexample, the capping group may be an organic acid residue of generalformula CH₃(W¹)_(q)CH₂(W²)_(p)CH₂(W³)_(z)—C(O)—O—, i.e., as reflected inFormula I. In certain embodiments, the “cap” or “capping group” is afatty acid. In certain embodiments, the capping group, regardless ofsize, is substituted or unsubstituted, saturated or unsaturated, and/orbranched or unbranched. For example, in certain embodiments, the cap isepoxidized or sulfurized, and is thus substituted with at least oneoxygen or at least one sulfur, respectively. The cap or capping materialmay also be referred to as the primary or alpha (α) chain.

Depending on the manner in which the estolide is synthesized, the cap orcapping group alkyl may be the only alkyl from an organic acid residuein the resulting estolide that is unsaturated. In certain embodiments,it may be desirable to use a saturated organic or fatty-acid cap toincrease the overall saturation of the estolide and/or to increase theresulting estolide's stability. For example, in certain embodiments, itmay be desirable to provide a method of providing a saturated cappedestolide by epoxidizing, sulfurizing, and/or hydrogenating anunsaturated cap using any suitable methods available to those ofordinary skill in the art. Epoxidizing, sulfurizing, and/orhydrogenating may be used with various sources of the fatty-acidfeedstock, which may include mono- and/or polyunsaturated fatty acids.Without being bound to any particular theory, in certain embodiments,epoxidizing the estolide may help to improve the solubility and/ormiscibility of the compound in certain compositions, such as thosecontaining polymeric materials. Without being bound to any particulartheory, in certain embodiments, sulfurizing the estolide may help toimprove the frictional properties of the compound, and thus may beuseful in providing wear and extreme pressure properties to lubricantcompositions. Without being bound to any particular theory, in certainembodiments, hydrogenating the estolide may help to improve the overallstability of the molecule. However, a fully-hydrogenated estolide, suchas an estolide with a larger fatty acid cap, may exhibit increased pourpoint temperatures. In certain embodiments, it may be desirable tooffset any loss in desirable pour-point characteristics by usingshorter, saturated capping materials.

The R₄C(O)O— of Formula II, the structure CH₃(W⁶)_(y)CH(W⁷)—C(O)O— ofFormula I, or the structure CH₃(CH₂)_(y)CH(CH₂)—C(O)O— of Formula IIIserve as the “base” or “base chain residue” of the estolide. Dependingon the manner in which the estolide is synthesized, the base organicacid or fatty acid residue may be the only residue that remains in itsfree-acid form after the initial synthesis of the estolide. However, incertain embodiments, in an effort to alter or improve the properties ofthe estolide, the free acid may be reacted with any number ofsubstituents. For example, it may be desirable to react the free acidestolide with alcohols, glycols, amines, or other suitable reactants toprovide the corresponding ester, amide, or other reaction products. Thebase or base chain residue may also be referred to as tertiary or gamma(γ) chains.

The R₃C(O)O— of Formula II, CH₃(CH₂)_(y)CH(CH₂)—C(O)O— of Formula III,and CH₃(W⁴)_(y)CH(W⁵)—C(O)O— of Formula I are linking residues that linkthe capping material and the base fatty-acid residue together. There maybe any number of linking residues in the estolide, including when n=0and the estolide is in its dimer form. Depending on the manner in whichthe estolide is prepared, a linking residue may be a fatty acid and mayinitially be in an unsaturated form during synthesis. In someembodiments, the estolide will be formed when a catalyst is used toproduce a carbocation at the fatty acid's site of unsaturation, which isfollowed by nucleophilic attack on the carbocation by the carboxylicgroup of another fatty acid. In some embodiments, it may be desirable tohave a linking fatty acid that is monounsaturated so that when the fattyacids link together, all of the sites of unsaturation are eliminated.The linking residue(s) may also be referred to as secondary or beta (β)chains.

In certain embodiments, the linking residues present in an estolidediffer from one another. In certain embodiments, one or more of thelinking residues differs from the base chain residue.

As noted above, in certain embodiments, suitable unsaturated fatty acidsfor preparing the estolides may include any mono- or polyunsaturatedfatty acid. For example, monounsaturated fatty acids, along with asuitable catalyst, will form a single carbocation that allows for theaddition of a second fatty acid, whereby a single link between two fattyacids is formed. Suitable monounsaturated fatty acids may include, butare not limited to, palmitoleic acid (16:1), vaccenic acid (18:1), oleicacid (18:1), eicosenoic acid (20:1), erucic acid (22:1), and nervonicacid (24:1). In addition, in certain embodiments, polyunsaturated fattyacids may be used to create estolides. Suitable polyunsaturated fattyacids may include, but are not limited to, hexadecatrienoic acid (16:3),alpha-linolenic acid (18:3), stearidonic acid (18:4), eicosatrienoicacid (20:3), eicosatetraenoic acid (20:4), eicosapentaenoic acid (20:5),heneicosapentaenoic acid (21:5), docosapentaenoic acid (22:5),docosahexaenoic acid (22:6), tetracosapentaenoic acid (24:5),tetracosahexaenoic acid (24:6), linoleic acid (18:2), gamma-linoleicacid (18:3), eicosadienoic acid (20:2), dihomo-gamma-linolenic acid(20:3), arachidonic acid (20:4), docosadienoic acid (20:2), adrenic acid(22:4), docosapentaenoic acid (22:5), tetracosatetraenoic acid (22:4),tetracosapentaenoic acid (24:5), pinolenic acid (18:3), podocarpic acid(20:3), rumenic acid (18:2), alpha-calendic acid (18:3), beta-calendicacid (18:3), jacaric acid (18:3), alpha-eleostearic acid (18:3),beta-eleostearic (18:3), catalpic acid (18:3), punicic acid (18:3),rumelenic acid (18:3), alpha-parinaric acid (18:4), beta-parinaric acid(18:4), and bosseopentaenoic acid (20:5). In certain embodiments,hydroxy fatty acids may be polymerized or homopolymerized by reactingthe carboxylic acid functionality of one fatty acid with the hydroxyfunctionality of a second fatty acid. Exemplary hydroxyl fatty acidsinclude, but are not limited to, ricinoleic acid, 6-hydroxystearic acid,9,10-dihydroxystearic acid, 12-hydroxystearic acid, and14-hydroxystearic acid.

The process for preparing the estolide compounds described herein mayinclude the use of any natural or synthetic fatty acid source. However,it may be desirable to source the fatty acids from a renewablebiological feedstock. Suitable starting materials of biological originmay include plant fats, plant oils, plant waxes, animal fats, animaloils, animal waxes, fish fats, fish oils, fish waxes, algal oils andmixtures thereof. Other potential fatty acid sources may include wasteand recycled food-grade fats and oils, fats, oils, and waxes obtained bygenetic engineering, fossil fuel-based materials and other sources ofthe materials desired.

In certain embodiments, the estolide compounds described herein may beprepared from non-naturally occurring fatty acids derived from naturallyoccurring feedstocks. In certain embodiments, the estolides are preparedfrom synthetic fatty acid reactants derived from naturally occurringfeedstocks such as vegetable oils. For example, the synthetic fatty acidreactants may be prepared by cleaving fragments from larger fatty acidresidues occurring in natural oils such as triglycerides using, forexample, a cross-metathesis catalyst and alpha-olefin(s). The resultingtruncated fatty acid residue(s) may be liberated from the glycerinebackbone using any suitable hydrolytic and/or transesterificationprocesses known to those of skill in the art. An exemplary fatty acidreactant includes 9-dodecenoic acid, which may be prepared via the crossmetathesis of an oleic acid residue with 1-butene.

In certain embodiments, the estolide comprises fatty-acid chains ofvarying lengths. In some embodiments, z, p, and q are integersindependently selected from 0 to 15, 0 to 12, 0 to 8, 0 to 6, 0 to 4,and 0 to 2. For example, in some embodiments, z is an integer selectedfrom 0 to 15, 0 to 12, and 0 to 8. In some embodiments, z is an integerselected from 2 to 8. In some embodiments, z is 6. In some embodiments,p is an integer selected from 0 to 15, 0 to 6, and 0 to 3. In someembodiments, p is an integer selected from 1 to 5. In some embodiments,p is an integer selected from 1, 2, and 3, or 4, 5, and 6. In someembodiments, p is 1. In some embodiments, q is an integer selected from0 to 15, 0 to 10, 0 to 6, and 0 to 3. In some embodiments, q is aninteger selected from 1 to 8. In some embodiments, q is an integerselected from 0 and 1, 2 and 3, or 5 and 6. In some embodiments, q is 6.In some embodiments, z, p and q, independently for each occurrence, areselected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and 15.In some embodiments, z+p+q is an integer selected from 12 to 20. In someembodiments, z+p+q is 14. In some embodiments, z+p+q is 13.

In some embodiments, the estolide comprises fatty-acid chains of varyinglengths. In some embodiments, x is, independently for each occurrence,an integer selected from 0 to 20, 0 to 18, 0 to 16, 0 to 14, 1 to 12, 1to 10, 2 to 8, 6 to 8, or 4 to 6. In some embodiments, x is,independently for each occurrence, an integer selected from 7 and 8. Insome embodiments, x is, independently for each occurrence, an integerselected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,17, 18, 19, and 20. In certain embodiments, for at least one fatty acidchain residue, x is an integer selected from 7 and 8.

In some embodiments, y is, independently for each occurrence, an integerselected from 0 to 20, 0 to 18, 0 to 16, 0 to 14, 1 to 12, 1 to 10, 2 to8, 6 to 8, or 4 to 6. In some embodiments, y is, independently for eachoccurrence, an integer selected from 7 and 8. In some embodiments, y is,independently for each occurrence, an integer selected from 0, 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20. Insome embodiments, for at least one fatty acid chain residue, y is aninteger selected from 0 to 6, or 1 and 2. In certain embodiments, y is,independently for each occurrence, an integer selected from 1 to 6, or 1and 2.

In some embodiments, x+y is, independently for each chain, an integerselected from 0 to 40, 0 to 20, 10 to 20, or 12 to 18. In someembodiments, x+y is, independently for each chain, an integer selectedfrom 13 to 15. In some embodiments, x+y is 15 for each chain. In someembodiments, x+y is, independently for each chain, an integer selectedfrom 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23,and 24. In certain embodiments, for at least one fatty acid chainresidue, x+y is an integer selected from 9 to 13. In certainembodiments, for at least one fatty acid chain residue, x+y is 9. Incertain embodiments, x+y is, independently for each chain, an integerselected from 9 to 13. In certain embodiments, x+y is 9 for each fattyacid chain residue.

In some embodiments, W¹, W², W³, W⁴, W⁵, W⁶, and W⁷, independently foreach occurrence, are selected from —CH₂—, —CH═CH—, —CHR₅—, and

wherein T is selected from O and S, R₅ is selected from a halogen and—S_(v)R₆, v is an integer selected from 1 to 8, and R₆ is selected fromhydrogen and an estolide residue. As used herein, the term “estolideresidue” refers to a portion of the same estolide molecule, or a portionof a different estolide molecule, to which one or more groups are bound.For example, in certain embodiments where the group W² for a compound ofFormula I is the group —CHR₅—, and R₅ is —S_(v)R₆, the group R₆ mayrepresent a second estolide molecule that is covalently bound to thegroup —S_(v)— (sulfide group), wherein the resulting structurecomprises:

Alternatively, the R₆ group may represent the same estolide molecule,wherein the sulfide group provides an intramolecular linkage within theestolide molecule itself (e.g., —S_(v)— linkage between two fatty acidresidue chains, such as between W² and W⁴), wherein the resultingstructure comprises:

In certain embodiments, when a compound of Formula I comprises more thanone —CHR₅—, said compound may comprise a combination of the priorexamples and, e.g., may exhibit one or more intramolecular and/orintermolecular sulfide linkages.

In certain embodiments, W³ is —CH₂—. In certain embodiments, W¹ is—CH₂—. In certain embodiments, W³, W⁵, and W⁷ for each occurrence are—CH₂—. In some embodiments, W⁴ and W⁶ for each occurrence are —CH₂—. Incertain embodiments, at least one of W¹, W², W³, W⁴, W⁵, W⁶, or W⁷ isselected from

In certain embodiments, W² is selected from —CHR₅— and

In certain embodiments, v is, independently for each occurrence, aninteger selected from 1 and 2. In certain embodiments, W² is selectedfrom

W¹, W³, W⁴, W⁵, and W⁶ are CH₂, x+y is 15 for each chain, z is 6, and qis 6.

In some embodiments, the estolide compound of Formula I, II, or III maycomprise any number of fatty acid residues to form an “n-mer” estolide.For example, the estolide may be in its dimer (n=0), trimer (n=1),tetramer (n=2), pentamer (n=3), hexamer (n=4), heptamer (n=5), octamer(n=6), nonamer (n=7), or decamer (n=8) form. In some embodiments, n isan integer selected from 0 to 20, 0 to 18, 0 to 16, 0 to 14, 0 to 12, 0to 10, 0 to 8, or 0 to 6. In some embodiments, n is an integer selectedfrom 0 to 4. In some embodiments, n is 1, wherein said at least onecompound of Formula I, II, or III comprises the trimer. In someembodiments, n is greater than 1. In some embodiments, n is an integerselected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,17, 18, 19, and 20.

In certain embodiments, the compounds of Formulas I and III representsubgenera of Formula II. Thus, in some embodiments, reference to acompound of Formulas I or III may also be described in reference toFormula II. By way of example, a compound of Formula I can be describedwith reference to Formula II, wherein m=1 and R₄ represents the groupCH₃(W¹)_(q)CH₂(W²)_(p)CH₂(W³)_(z)—.

In addition to being sulfurized and/or epoxidized, in certainembodiments, the capping group is an optionally substituted alkyl thatis saturated or unsaturated, and branched or unbranched. In someembodiments, the alkyl group is a C₁ to C₄₀ alkyl, C₁ to C₂₂ alkyl or C₁to C₁₈ alkyl. In some embodiments, the alkyl group is selected from C₇to C₁₇ alkyl. For example, with reference to Formula II, in certainembodiments R₁ is selected from C₇ alkyl, C₉ alkyl, C₁₁ alkyl, C₁₃alkyl, C₁₅ alkyl, and C₁₇ alkyl. In some embodiments, R₁ is selectedfrom C₁₃ to C₁₇ alkyl, such as from C₁₃ alkyl, C₁₅ alkyl, and C₁₇ alkyl.In some embodiments, R₁ is a C₁, C₂, C₃, C₄, C_(s), C₆, C₇, C₈, C₉, C₁₀,C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈, C₁₉, C₂₀, C₂₁, or C₂₂ alkyl.

In some embodiments, R₂ of Formula I, II, or III is an optionallysubstituted alkyl that is saturated or unsaturated, and branched orunbranched. In some embodiments, the alkyl group is a C₁ to C₄₀ alkyl,C₁ to C₂₂ alkyl or C₁ to C₁₈ alkyl. In some embodiments, the alkyl groupis selected from C₇ to C₁₇ alkyl. In some embodiments, R₂ is selectedfrom C₇ alkyl, C₉ alkyl, C₁₁ alkyl, C₁₃ alkyl, C₁₅ alkyl, and C₁₇ alkyl.In some embodiments, R₂ is selected from C₁₃ to C₁₇ alkyl, such as fromC₁₃ alkyl, C₁₅ alkyl, and C₁₇ alkyl. In some embodiments, R₂ is a C₁,C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇,C₁₈, C₁₉, C₂₀, C₂₁, or C₂₂ alkyl.

In some embodiments, R₃ is an optionally substituted alkyl that issaturated or unsaturated, and branched or unbranched. In someembodiments, the alkyl group is a C₁ to C₄₀ alkyl, C₁ to C₂₂ alkyl or C₁to C₁₈ alkyl. In some embodiments, the alkyl group is selected from C₇to C₁₇ alkyl. In some embodiments, R₃ is selected from C₇ alkyl, C₉alkyl, C₁₁ alkyl, C₁₃ alkyl, C₁₅ alkyl, and C₁₇ alkyl. In someembodiments, R₃ is selected from C₁₃ to C₁₇ alkyl, such as from C₁₃alkyl, C₁₅ alkyl, and C₁₇ alkyl. In some embodiments, R₃ is a C₁, C₂,C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈,C₁₉, C₂₀, C₂₁, or C₂₂ alkyl.

In some embodiments, R₄ is an optionally substituted alkyl that issaturated or unsaturated, and branched or unbranched. In someembodiments, the alkyl group is a C₁ to C₄₀ alkyl, C₁ to C₂₂ alkyl or C₁to C₁₈ alkyl. In some embodiments, the alkyl group is selected from C₇to C₁₇ alkyl. In some embodiments, R₄ is selected from C₇ alkyl, C₉alkyl, C₁₁ alkyl, C₁₃ alkyl, C₁₅ alkyl, and C₁₇ alkyl. In someembodiments, R₄ is selected from C₁₃ to C₁₇ alkyl, such as from C₁₃alkyl, C₁₅ alkyl, and C₁₇ alkyl. In some embodiments, R₄ is a C₁, C₂,C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈,C₁₉, C₂₀, C₂₁, or C₂₂ alkyl.

As noted above, in certain embodiments, it may be possible to manipulateone or more of the estolides' properties by altering the length of R₁and/or its degree of saturation. However, in certain embodiments, thelevel of substitution on R₁ may also be altered to change or evenimprove the estolides' properties. Without being bound to any particulartheory, in certain embodiments, it is believed that the presence ofpolar substituents on R₁, such as one or more hydroxy groups, mayincrease the viscosity of the estolide, while increasing pour point.Accordingly, in some embodiments, R₁ will be unsubstituted or optionallysubstituted with a group that is not hydroxyl. Alternatively, in someembodiments, it may be desirable to increase the overall polarity of themolecule by providing one or more polar substituents on R₁, such as oneor more epoxy groups, sulfur groups, and/or hydroxyl groups.

In some embodiments, the estolide is in its free-acid form, wherein R₂of Formula I, II, or III is hydrogen. In some embodiments, R₂ isselected from optionally substituted alkyl that is saturated orunsaturated, and branched or unbranched. In certain embodiments, the R₂residue may comprise any desired alkyl group, such as those derived fromesterification of the estolide with the alcohols identified in theexamples herein. In some embodiments, the alkyl group is selected fromC₁ to C₄₀, C₁ to C₂₂, C₃ to C₂₀, C₁ to C₁₈, or C₆ to C₁₂ alkyl. In someembodiments, R₂ may be selected from C₃ alkyl, C₄ alkyl, C₈ alkyl, C₁₂alkyl, C₁₆ alkyl, C₁₈ alkyl, and C₂₀ alkyl. For example, in certainembodiments, R₂ may be branched, such as isopropyl, isobutyl, or2-ethylhexyl. In some embodiments, R₂ may be a larger alkyl group,branched or unbranched, comprising C₁₂ alkyl, C₁₆ alkyl, C₁₈ alkyl, orC₂₀ alkyl. Such groups at the R₂ position may be derived fromesterification of the free-acid estolide using the Jarcol™ line ofalcohols marketed by Jarchem Industries, Inc. of Newark, N.J., includingJarcol™ I-18CG, I-20, I-12, I-16, I-18T, and 85BJ. In some cases, R₂ maybe sourced from certain alcohols to provide branched alkyls such asisostearyl and isopalmityl. It should be understood that suchisopalmityl and isostearyl alkyl groups may cover any branched variationof C₁₆ and C₁₈, respectively. For example, the estolides describedherein may comprise highly-branched isopalmityl or isostearyl groups atthe R₂ position, derived from the Fineoxocol® line of isopalmityl andisostearyl alcohols marketed by Nissan Chemical America Corporation ofHouston, Tex., including Fineoxocol® 180, 180N, and 1600. Without beingbound to any particular theory, in embodiments, large, highly-branchedalkyl groups (e.g., isopalmityl and isostearyl) at the R₂ position ofthe estolides can provide at least one way to increase the lubricant'sviscosity, while substantially retaining or even reducing its pourpoint.

In some embodiments, the compounds described herein may comprise amixture of two or more estolide compounds of Formula I, II, and III. Itis possible to characterize the chemical makeup of an estolide, amixture of estolides, or a composition comprising estolides, by usingthe compound's, mixture's, or composition's measured estolide number(EN) of compound or composition. The EN represents the average number offatty acids added to the base fatty acid. The EN also represents theaverage number of estolide linkages per molecule:

EN=n+1

wherein n is the number of secondary (β) fatty acids. Accordingly, asingle estolide compound will have an EN that is a whole number, forexample for dimers, trimers, and tetramers:

dimer EN=1

trimer EN=2

tetramer EN=3

However, a composition comprising two or more estolide compounds mayhave an EN that is a whole number or a fraction of a whole number. Forexample, a composition having a 1:1 molar ratio of dimer and trimerwould have an EN of 1.5, while a composition having a 1:1 molar ratio oftetramer and trimer would have an EN of 2.5.

In some embodiments, the compositions may comprise a mixture of two ormore estolides having an EN that is an integer or fraction of an integerthat is greater than 4.5, or even 5.0. In some embodiments, the EN maybe an integer or fraction of an integer selected from about 1.0 to about5.0. In some embodiments, the EN is an integer or fraction of an integerselected from 1.2 to about 4.5. In some embodiments, the EN is selectedfrom a value greater than 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6,2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, 5.0, 5.2, 5.4,5.6 and 5.8. In some embodiments, the EN is selected from a value lessthan 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6,3.8, 4.0, 4.2, 4.4, 4.6, 4.8, and 5.0, 5.2, 5.4, 5.6, 5.8, and 6.0. Insome embodiments, the EN is selected from 1, 1.2, 1.4, 1.6, 1.8, 2.0,2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8,5.0, 5.2, 5.4, 5.6, 5.8, and 6.0.

As noted above, it should be understood that the chains of the estolidecompounds may be independently optionally substituted, wherein one ormore hydrogens are removed and replaced with one or more of thesubstituents identified herein. Similarly, two or more of the hydrogenresidues may be removed to provide one or more sites of unsaturation,such as a cis or trans double bond. Further, the chains may optionallycomprise branched hydrocarbon residues. For example, in some embodimentsthe estolides described herein may comprise at least one compound ofFormula II:

-   -   wherein    -   m is an integer equal to or greater than 1;    -   n is an integer equal to or greater than 0;    -   R₁, independently for each occurrence, is an optionally        substituted alkyl that is saturated or unsaturated, and branched        or unbranched    -   R₂ is selected from hydrogen and optionally substituted alkyl        that is saturated or unsaturated, and branched or unbranched;        and    -   R₃ and R₄, independently for each occurrence, are selected from        optionally substituted alkyl that is saturated or unsaturated,        and branched or unbranched,    -   wherein at least one of R₁, R₃, or R₄ comprises an unbranched        undecanyl that is saturated or unsaturated.

In certain embodiments, m is 1. In some embodiments, m is an integerselected from 2, 3, 4, and 5. In some embodiments, n is an integerselected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12. In someembodiments, one or more R₃ differs from one or more other R₃ in acompound of Formula II. In some embodiments, one or more R₃ differs fromR₄ in a compound of Formula II. In some embodiments, if the compounds ofFormula II are prepared from one or more polyunsaturated fatty acids, itis possible that one or more of R₃ and R₄ will have one or more sites ofunsaturation. Accordingly, in certain embodiments, estolides havingmultiple sites of unsaturation may be epoxidized and/or sulfurized toprovide estolides having multiple sites of epoxidation or sulfurization.In some embodiments, if the compounds of Formula II are prepared fromone or more branched fatty acids, it is possible that one or more of R₃and R₄ will be branched.

In some embodiments, R₃ and R₄ can be CH₃(CH₂)_(y)CH(CH₂)_(x)—, where xis, independently for each occurrence, an integer selected from 0, 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20, andy is, independently for each occurrence, an integer selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.Where both R₃ and R₄ are CH₃(CH₂)_(y)CH(CH₂)—, the compounds may becompounds according to Formula III.

Without being bound to any particular theory, in certain embodiments,altering the EN produces estolides having desired viscometric propertieswhile substantially retaining or even reducing pour point. For example,in some embodiments the estolides exhibit a decreased pour point uponincreasing the EN value. Accordingly, in certain embodiments, a methodis provided for retaining or decreasing the pour point of an estolidebase oil by increasing the EN of the base oil, or a method is providedfor retaining or decreasing the pour point of a composition comprisingan estolide base oil by increasing the EN of the base oil. In someembodiments, the method comprises: selecting an estolide base oil havingan initial EN and an initial pour point; and removing at least a portionof the base oil, said portion exhibiting an EN that is less than theinitial EN of the base oil, wherein the resulting estolide base oilexhibits an EN that is greater than the initial EN of the base oil, anda pour point that is equal to or lower than the initial pour point ofthe base oil. In some embodiments, the selected estolide base oil isprepared by oligomerizing at least one first unsaturated fatty acid withat least one second unsaturated fatty acid and/or saturated fatty acid.In some embodiments, the removing at least a portion of the base oil isaccomplished by distillation, chromatography, membrane separation, phaseseparation, affinity separation, solvent extraction, or combinationsthereof. In some embodiments, the distillation takes place at atemperature and/or pressure that is suitable to separate the estolidebase oil into different “cuts” that individually exhibit different ENvalues. In some embodiments, this may be accomplished by subjecting thebase oil temperature of at least about 250° C. and an absolute pressureof no greater than about 25 microns. In some embodiments, thedistillation takes place at a temperature range of about 250° C. toabout 310° C. and an absolute pressure range of about 10 microns toabout 25 microns.

In some embodiments, estolide compounds and compositions exhibit an ENthat is greater than or equal to 1, such as an integer or fraction of aninteger selected from about 1.0 to about 2.0. In some embodiments, theEN is an integer or fraction of an integer selected from about 1.0 toabout 1.6. In some embodiments, the EN is a fraction of an integerselected from about 1.1 to about 1.5. In some embodiments, the EN isselected from a value greater than 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6,1.7, 1.8, and 1.9. In some embodiments, the EN is selected from a valueless than 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0.

In some embodiments, the EN is greater than or equal to 1.5, such as aninteger or fraction of an integer selected from about 1.8 to about 2.8.In some embodiments, the EN is an integer or fraction of an integerselected from about 2.0 to about 2.6. In some embodiments, the EN is afraction of an integer selected from about 2.1 to about 2.5. In someembodiments, the EN is selected from a value greater than 1.8, 1.9, 2.0,2.1, 2.2, 2.3, 2.4, 2.5, 2.6, and 2.7. In some embodiments, the EN isselected from a value less than 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6,2.7, and 2.8. In some embodiments, the EN is about 1.8, 2.0, 2.2, 2.4,2.6, or 2.8.

In some embodiments, the EN is greater than or equal to about 4, such asan integer or fraction of an integer selected from about 4.0 to about5.0. In some embodiments, the EN is a fraction of an integer selectedfrom about 4.2 to about 4.8. In some embodiments, the EN is a fractionof an integer selected from about 4.3 to about 4.7. In some embodiments,the EN is selected from a value greater than 4.0, 4.1, 4.2, 4.3, 4.4,4.5, 4.6, 4.7, 4.8, and 4.9. In some embodiments, the EN is selectedfrom a value less than 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, and5.0. In some embodiments, the EN is about 4.0, 4.2, 4.4, 4.6, 4.8, or5.0.

In some embodiments, the EN is greater than or equal to about 5, such asan integer or fraction of an integer selected from about 5.0 to about6.0. In some embodiments, the EN is a fraction of an integer selectedfrom about 5.2 to about 5.8. In some embodiments, the EN is a fractionof an integer selected from about 5.3 to about 5.7. In some embodiments,the EN is selected from a value greater than 5.0, 5.1, 5.2, 5.3, 5.4,5.5, 5.6, 5.7, 5.8, and 5.9. In some embodiments, the EN is selectedfrom a value less than 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, and6.0. In some embodiments, the EN is about 5.0, 5.2, 5.4, 5.4, 5.6, 5.8,or 6.0.

In some embodiments, the EN is greater than or equal to 1, such as aninteger or fraction of an integer selected from about 1.0 to about 2.0.In some embodiments, the EN is a fraction of an integer selected fromabout 1.1 to about 1.7. In some embodiments, the EN is a fraction of aninteger selected from about 1.1 to about 1.5. In some embodiments, theEN is selected from a value greater than 1.0, 1.1, 1.2, 1.3, 1.4, 1.5,1.6, 1.7, 1.8, or 1.9. In some embodiments, the EN is selected from avalue less than 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0. In someembodiments, the EN is about 1.0, 1.2, 1.4, 1.6, 1.8, or 2.0. In someembodiments, the EN is greater than or equal to 1, such as an integer orfraction of an integer selected from about 1.2 to about 2.2. In someembodiments, the EN is an integer or fraction of an integer selectedfrom about 1.4 to about 2.0. In some embodiments, the EN is a fractionof an integer selected from about 1.5 to about 1.9. In some embodiments,the EN is selected from a value greater than 1.0, 1.1, 1.2, 1.3, 1.4,1.5, 1.6, 1.7, 1.8, 1.9, 2.0, and 2.1. In some embodiments, the EN isselected from a value less than 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9,2.0, 2.1, and 2.2. In some embodiments, the EN is about 1.0, 1.2, 1.4,1.6, 1.8, 2.0, or 2.2.

In some embodiments, the EN is greater than or equal to 2, such as aninteger or fraction of an integer selected from about 2.8 to about 3.8.In some embodiments, the EN is an integer or fraction of an integerselected from about 2.9 to about 3.5. In some embodiments, the EN is aninteger or fraction of an integer selected from about 3.0 to about 3.4.In some embodiments, the EN is selected from a value greater than 2.0,2.1, 2.2, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.4, 3.5, 3.6, and3.7. In some embodiments, the EN is selected from a value less than 2.2,2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6,3.7, and 3.8. In some embodiments, the EN is about 2.0, 2.2, 2.4, 2.6,2.8, 3.0, 3.2, 3.4, 3.6, or 3.8. Typically, base stocks and lubricantcompositions exhibit certain lubricity, viscosity, and/or pour pointcharacteristics. For example, in certain embodiments, suitable viscositycharacteristics of the base oil may range from about 10 cSt to about 250cSt at 40° C., and/or about 3 cSt to about 30 cSt at 100° C. In someembodiments, the compounds and compositions may exhibit viscositieswithin a range from about 50 cSt to about 150 cSt at 40° C., and/orabout 10 cSt to about 20 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities less than about 55 cSt at 40° C. or less than about 45 cStat 40° C., and/or less than about 12 cSt at 100° C. or less than about10 cSt at 100° C. In some embodiments, the estolide compounds andcompositions may exhibit viscosities within a range from about 25 cSt toabout 55 cSt at 40° C., and/or about 5 cSt to about 11 cSt at 100° C. Insome embodiments, the estolide compounds and compositions may exhibitviscosities within a range from about 35 cSt to about 45 cSt at 40° C.,and/or about 6 cSt to about 10 cSt at 100° C. In some embodiments, theestolide compounds and compositions may exhibit viscosities within arange from about 38 cSt to about 43 cSt at 40° C., and/or about 7 cSt toabout 9 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities less than about 120 cSt at 40° C. or less than about 100 cStat 40° C., and/or less than about 18 cSt at 100° C. or less than about17 cSt at 100° C. In some embodiments, the estolide compounds andcompositions may exhibit a viscosity within a range from about 70 cSt toabout 120 cSt at 40° C., and/or about 12 cSt to about 18 cSt at 100° C.In some embodiments, the estolide compounds and compositions may exhibitviscosities within a range from about 80 cSt to about 100 cSt at 40° C.,and/or about 13 cSt to about 17 cSt at 100° C. In some embodiments, theestolide compounds and compositions may exhibit viscosities within arange from about 85 cSt to about 95 cSt at 40° C., and/or about 14 cStto about 16 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities greater than about 180 cSt at 40° C. or greater than about200 cSt at 40° C., and/or greater than about 20 cSt at 100° C. orgreater than about 25 cSt at 100° C. In some embodiments, the estolidecompounds and compositions may exhibit a viscosity within a range fromabout 180 cSt to about 230 cSt at 40° C., and/or about 25 cSt to about31 cSt at 100° C. In some embodiments, estolide compounds andcompositions may exhibit viscosities within a range from about 200 cStto about 250 cSt at 40° C., and/or about 25 cSt to about 35 cSt at 100°C. In some embodiments, estolide compounds and compositions may exhibitviscosities within a range from about 210 cSt to about 230 cSt at 40°C., and/or about 28 cSt to about 33 cSt at 100° C. In some embodiments,the estolide compounds and compositions may exhibit viscosities within arange from about 200 cSt to about 220 cSt at 40° C., and/or about 26 cStto about 30 cSt at 100° C. In some embodiments, the estolide compoundsand compositions may exhibit viscosities within a range from about 205cSt to about 215 cSt at 40° C., and/or about 27 cSt to about 29 cSt at100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities less than about 45 cSt at 40° C. or less than about 38 cStat 40° C., and/or less than about 10 cSt at 100° C. or less than about 9cSt at 100° C. In some embodiments, the estolide compounds andcompositions may exhibit a viscosity within a range from about 20 cSt toabout 45 cSt at 40° C., and/or about 4 cSt to about 10 cSt at 100° C. Insome embodiments, the estolide compounds and compositions may exhibitviscosities within a range from about 28 cSt to about 38 cSt at 40° C.,and/or about 5 cSt to about 9 cSt at 100° C. In some embodiments, theestolide compounds and compositions may exhibit viscosities within arange from about 30 cSt to about 35 cSt at 40° C., and/or about 6 cSt toabout 8 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities less than about 80 cSt at 40° C. or less than about 70 cStat 40° C., and/or less than about 14 cSt at 100° C. or less than about13 cSt at 100° C. In some embodiments, the estolide compounds andcompositions may exhibit a viscosity within a range from about 50 cSt toabout 80 cSt at 40° C., and/or about 8 cSt to about 14 cSt at 100° C. Insome embodiments, the estolide compounds and compositions may exhibitviscosities within a range from about 60 cSt to about 70 cSt at 40° C.,and/or about 9 cSt to about 13 cSt at 100° C. In some embodiments, theestolide compounds and compositions may exhibit viscosities within arange from about 63 cSt to about 68 cSt at 40° C., and/or about 10 cStto about 12 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities greater than about 120 cSt at 40° C. or greater than about130 cSt at 40° C., and/or greater than about 15 cSt at 100° C. orgreater than about 18 cSt at 100° C. In some embodiments, the estolidecompounds and compositions may exhibit a viscosity within a range fromabout 120 cSt to about 150 cSt at 40° C., and/or about 16 cSt to about24 cSt at 100° C. In some embodiments, the estolide compounds andcompositions may exhibit viscosities within a range from about 130 cStto about 160 cSt at 40° C., and/or about 17 cSt to about 28 cSt at 100°C. In some embodiments, the estolide compounds and compositions mayexhibit viscosities within a range from about 130 cSt to about 145 cStat 40° C., and/or about 17 cSt to about 23 cSt at 100° C. In someembodiments, the estolide compounds and compositions may exhibitviscosities within a range from about 135 cSt to about 140 cSt at 40°C., and/or about 19 cSt to about 21 cSt at 100° C. In some embodiments,the estolide compounds and compositions may exhibit viscosities of about1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20,21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 32, 34, 36, 38, 40, 42, 44, 46,48, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140,150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280,290, 300, 350, or 400 cSt. at 40° C. In some embodiments, the estolidecompounds and compositions may exhibit viscosities of about 1, 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23,24, 25, 26, 27, 28, 29, and 30 cSt at 100° C. In certain embodiments,estolides may exhibit desirable low-temperature pour point properties.In some embodiments, the estolide compounds and compositions may exhibita pour point lower than about −25° C., about −35° C., −40° C., or evenabout −50° C. In some embodiments, the estolide compounds andcompositions have a pour point of about −25° C. to about −45° C. In someembodiments, the pour point falls within a range of about −30° C. toabout −40° C., about −34° C. to about −38° C., about −30° C. to about−45° C., −35° C. to about −45° C., 34° C. to about −42° C., about −38°C. to about −42° C., or about 36° C. to about −40° C. In someembodiments, the pour point falls within the range of about −27° C. toabout −37° C., or about −30° C. to about −34° C. In some embodiments,the pour point falls within the range of about −25° C. to about −35° C.,or about −28° C. to about −32° C. In some embodiments, the pour pointfalls within the range of about −28° C. to about −38° C., or about −31°C. to about −35° C. In some embodiments, the pour point falls within therange of about −31° C. to about −41° C., or about −34° C. to about −38°C. In some embodiments, the pour point falls within the range of about−40° C. to about −50° C., or about −42° C. to about −48° C. In someembodiments, the pour point falls within the range of about −50° C. toabout −60° C., or about −52° C. to about −58° C. In some embodiments,the upper bound of the pour point is less than about −35° C., about −36°C., about −37° C., about −38° C., about −39° C., about −40° C., about−41° C., about −42° C., about −43° C., about −44° C., or about −45° C.In some embodiments, the lower bound of the pour point is greater thanabout −70° C., about −69° C., about −68° C., about −67° C., about −66°C., about −65° C., about −64° C., about −63° C., about −62° C., about−61° C., about −60° C., about −59° C., about −58° C., about −57° C.,about −56° C., −55° C., about −54° C., about −53° C., about −52° C.,−51, about −50° C., about −49° C., about −48° C., about −47° C., about−46° C., or about −45° C.

In addition, in certain embodiments, the estolides may exhibit decreasedIodine Values (IV) when compared to estolides prepared by other methods.IV is a measure of the degree of total unsaturation of an oil, and isdetermined by measuring the amount of iodine per gram of estolide(cg/g). In certain instances, oils having a higher degree ofunsaturation may be more susceptible to creating corrosiveness anddeposits, and may exhibit lower levels of oxidative stability. Compoundshaving a higher degree of unsaturation will have more points ofunsaturation for iodine to react with, resulting in a higher IV. Thus,in certain embodiments, it may be desirable to reduce the IV ofestolides in an effort to increase the oil's oxidative stability, whilealso decreasing harmful deposits and the corrosiveness of the oil.

In some embodiments, estolide compounds and compositions describedherein have an IV of less than about 40 cg/g or less than about 35 cg/g.In some embodiments, estolides have an IV of less than about 30 cg/g,less than about 25 cg/g, less than about 20 cg/g, less than about 15cg/g, less than about 10 cg/g, or less than about 5 cg/g. The IV of acomposition may be reduced by decreasing the estolide's degree ofunsaturation. This may be accomplished by, for example, by increasingthe amount of saturated capping materials relative to unsaturatedcapping materials when synthesizing the estolides. Alternatively, incertain embodiments, IV may be reduced by hydrogenating estolides havingunsaturated caps.

In certain embodiments, the estolides described herein may be suitablefor use as anti-wear and/or extreme pressure agents. In certainembodiments, the anti-wear and/or extreme pressure agent comprises atleast one sulfurized estolide. In certain embodiments, the at least onesulfurized estolide is a component of a lubricating composition, such asa grease or a motor oil. In certain embodiments, the lubricatingcomposition further comprises at least one base oil, such as apetroleum-derived base oil. In certain embodiments, the base oilcomprises at least one estolide that is not sulfurized. In certainembodiments, the lubricating composition further comprises at least oneadditive. In certain embodiments, the at least one additive comprisesone or more compounds selected from separation preventers, stabilityenhancers, biocides, surfactants, corrosion inhibitors, antioxidants,abrasion inhibitors, viscosity index improvers, pour-point depressants,detergent-dispersants, and antifoaming agents.

In certain embodiments, sulfurized estolides may be prepared bysulfurizing one or more estolide compounds having at least one site ofunsaturation. In certain embodiments, the sulfurizing may beaccomplished by any method known to those of ordinary skill in the art,such as direct sulfurization utilizing elemental sulfur. Other exemplarysulfurizing methods include, but are not limited to, those utilizing oneor more compounds selected from sulfur monochloride, sulfur dichloride,sodium sulfide/H₂S/sulfur, sodium sulfide/H₂S, sodium sulfide/sodiummercaptide/sulfur, and sulfurization utilizing a chain transfer agent.

In certain embodiments, the lubricating composition comprises at leastone sulfurized estolide and at least one base oil. In certainembodiments, the mass ratio of the at least one sulfurized estolide tothe at least one base oil is about 99:1 to about 1:99. In certainembodiments, the mass ratio of the at least one sulfurized estolidecompound to the at least one base oil is about 95:5, 90:10, 85:15,80:20, 75:25, 70:30, 65:35, 60:40, 55:45, 50:50, 45:55, 40:60, 35:65,30:70, 25:75, 20:80, 15:85, 10:90, or 5:95. In certain embodiments, thelubricating composition comprises from about 0 wt. % to about 95 wt. %,such as about 1 wt. % to about 80 wt. %, about 1 wt. % to about 70 wt. %or about 1 wt. % to about 50 wt. % of the at least one sulfurizedestolide compound. In certain embodiments, the at least one sulfurizedestolide compound is present in amounts of about 0 to about 30 wt. % ofthe lubricating composition. In certain embodiments, the at least onesulfurized estolide compound is present in amounts of about 0 to about20, about 0 to about 15, about 0 to about 10, about 0 to about 8, about0 to about 6, about 0 to about 4, or about 0 to about 2 wt. % of thelubricating composition. In certain embodiments, the at least onesulfurized estolide compound is present in amounts of about 0 to about 5wt. % of the lubricating composition, such as about 0.1 to about 3 wt %or 0.01 to about 1 wt. %. In certain embodiments, the at least onesulfurized estolide compound is present in amounts of about 0.2, 0.4,0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, or 3.0 wt. %of the lubricating composition. In certain embodiments, the at least onesulfurized estolide compound is present in amounts of about 0.01, 0.02,0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, or 0.1 wt. % of thelubricating composition.

In certain embodiments are described compositions comprising at leastone epoxidized estolide compound. In certain embodiments, thecomposition is a plasticized composition. In certain embodiments, theplasticized composition further comprises at least one polymericmaterial. In certain embodiments, the plasticized composition maycomprise a solid, semi-solid, or liquid composition. In certainembodiments, the plasticized composition may be referred to as aplastisol. In certain embodiments, the plastisol comprises a polymericmaterial (e.g., non-crosslinked organic polymer) and a liquid phase(e.g., epoxidized estolide and/or a diluent).

In certain embodiments, epoxidized estolides can be prepared byepoxidizing one or more estolide compounds having at least one site ofunsaturation. In certain embodiments, the epoxidizing may beaccomplished using any of the methods generally known to those ofordinary skill in the art, such as using hydrogen peroxide and/or formicacid, or those methods involving one or more percarboxylic acids such asm-chloroperbenzoic acid, peracetic acid, or performic acid. Exemplaryepoxidation methods also include those set forth in D. Swern, OrganicPeroxides, Volume 2, 355-533, Interscience Publishers, 1971, which isincorporated by reference in its entirety for all purposes.

As used herein, the term “polymeric material” means any synthetic ornaturally-occurring polymeric material, including copolymers andhomopolymers. In certain embodiments, the at least one polymericmaterial comprises one or more compounds selected from polyvinylpolymers, polyolefins, acrylate polymers, methacrylate polymers, styrenepolymers, polyesters, polyamides, polycarbonates, polyurethanes,polysulfides, silicones, elastomers, and rubbers. In certainembodiments, the mass ratio of the at least one epoxidized estolidecompound to the at least one polymeric material is about 99:1 to about1:99. In certain embodiments, the mass ratio of the at least oneepoxidized estolide compound to the at least one polymeric material isabout 95:5, 90:10, 85:15, 80:20, 75:25, 70:30, 65:35, 60:40, 55:45,50:50, 45:55, 40:60, 35:65, 30:70, 25:75, 20:80, 15:85, 10:90, or 5:95.In certain embodiments, the plasticized composition comprises from about0 wt. % to about 95 wt. %, such as about 1 wt. % to about 80 wt. %,about 1 wt. % to about 70 wt. % or about 1 wt. % to about 50 wt. % ofthe at least one polymeric material. In certain embodiments, the atleast one polymeric material is present in amounts of about 1 wt. % toabout 30 wt. %, about 1 wt. % to about 25 wt. %, or about 0.1 wt. % toabout 20 wt. % of the plasticized composition. In certain embodiments,the at least one polymeric material comprises about 0.5, 1, 1.5, 2, 2.5,3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 11, 12, 13,14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 30, 35, 40, 45, 50, 55,60, 65, 70, 75, or 80 wt. % of the plasticized composition.

As used herein, polymeric materials may comprise homopolymers orcopolymers. Accordingly, unless indicated otherwise, it should beunderstood that reference to a polymer such as polyethylene includes,but is not limited to, a polyethylene homopolymer and a copolymercomprising ethylene monomers and at least one non-ethylene monomer(e.g., vinyl acetate). Exemplary polymeric materials include, but arenot limited to, polyvinyl chlorides (PVC), polyethylenes,polypropylenes, polybutylenes, poly(ester amide),polystyrene-polyisobutylene-polystyrene block copolymer (SIS),polystyrene, polyisobutylene, polycaprolactone (PCL), poly(L-lactide),poly(D,L-lactide), polylactic acid (PLA), poly(lactide-co-glycolide),poly(glycolide), polyalkylene, polyfluoroalkylene, polyhydroxyalkanoate,poly(3-hydroxybutyrate), poly(4-hydroxybutyrate),poly(3-hydroxyvalerate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate),poly(3-hydroxyhexanoate), poly(4-hydroxyhexanoate), mid-chainpolyhydroxyalkanoate, poly(trimethylene carbonate), poly(orthoester),polyphosphazenes, poly(phosphoester), poly(tyrosine derived arylates),poly(tyrosine derived carbonates), polydimethyloxanone (PDMS),polyvinylidene fluoride (PVDF), polyhexafluoropropylene (HFP),polydimethylsiloxane, poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP), poly(vinylidene fluoride-co-chlorotrifluoroethylene)(PVDF-CTFE), poly(butyl methacrylate), poly(methyl methacrylate),poly(methacrylates), poly(vinyl acetate), poly(ethylene-co-vinylacetate), poly(ethylene-co-vinyl alcohol), poly(ester urethanes),poly(ether-urethanes), poly(carbonate-urethanes),poly(silicone-urethanes), poly(2-hydroxyethyl methacrylate), Solef™ PVDF(polyvinylidene fluoride), poly(urea-urethanes), hydroxylethylmethacrylate (HEMA), hydroxypropyl methacrylate (HPMA),hydroxypropylmethacrylamide, alkoxymethacrylate, alkoxyacrylate,3-trimethylsilylpropyl methacrylate (TMSPMA), poly(methyl methacrylate)(PMMA), poly(ethylene glycol) (PEG), polypropylene glycol) (PPG), PEGacrylate (PEGA), PEG methacrylate, methacrylic acid (MA), ethylene-vinylacetate, acrylic acid (AA), SIS-PEG, polystyrene-PEG,polyisobutylene-PEG, PCL-PEG, PLA-PEG, PMMA-PEG, PDMS-PEG, PVDF-PEG,poly(tetramethylene glycol), polyhydroxyalkanoates (PHAs), poly(esteramides), polycaprolactones, poly(L-lactide), poly(D,L-lactide),poly(D,L-lactide-co-PEG) block copolymers,poly(D,L-lactide-co-trimethylene carbonate), polyglycolides,poly(lactide-co-glycolide), polydioxanones, polyorthoesters,polyanhydrides, poly(glycolic acid-co-trimethylene carbonate),polyphosphoesters, polyphosphoester urethanes, poly(amino acids),polycyanoacrylates, poly(trimethylene carbonate), poly(imino carbonate),polycarbonates, polyurethanes, copoly(ether-esters) (e.g., PEO/PLA),polyalkylene oxalates, polyphosphazenes, PHA-PEG,poly(alpha-hydroxyacids), poly(beta-hydroxyacids) such aspoly(-hydroxybutyrate) (PHB), poly(3-hydroxybutyrate-co-valerate)(PHBV), poly(3-hydroxypropionate) (PHP), poly(3-hydroxyhexanoate) (PHH),a poly(4-hydroxyacid) such as poly(4-hydroxybutyrate),poly(4-hydroxyvalerate), or poly(4-hydroxyhexanoate),poly(hydroxyvalerate), polyanhydrides, poly(hydroxyethyl methacylate),poly(N-acylhydroxyproline)esters, poly(N-palmitoylhydroxyproline)esters, polyphosphazenes, poly(tyrosine carbonates), andpoly(tyrosine arylates).

In certain embodiments, the at least one polymeric material isbiodegradable. In certain embodiments, the biodegradable polymericmaterial comprises one or more materials selected from biodegradablepolyesters and biodegradable polyethylenes. Exemplary biodegradablepolyesters include, but are not limited to, polyglycolic acid,polylactic acid, polycaprolactone, polyhydroxybutyrate,polyhydroxyvalerate, and polyhydroxyvaleric acid. Exemplarybiodegradable polyethylenes include, but are not limited to,polyvinylacetate, poly(butylenes succinate), polyvinyl alcohol, andpoly-p-dioxanone.

Exemplary elastomers and rubbers include, but are not limited to,natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR),1,2-butadiene rubber, styrene-butadiene rubber (SBR),acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), butylrubber (BR), ethylene-propylene-diene rubber (EPDM) and other dienerubbers and their hydrogenated products, ethylene-propylene rubber(EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM),chlorosulfonated polyethylene, acrylic rubber, fluororubber,polyethylene rubber, polypropylene rubber, and other olefin rubbers,epichlorohydrin rubbers, polysulfide rubbers, silicone rubbers, andurethane rubbers. In certain embodiments, the elastomer may comprise aresin component. Exemplary elastomers may include optionallyhydrogenated polystyrene elastomeric polymers (e.g.,styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), andstyrene-ethylene/butylene-styrene (SEBS)), polyolefin elastomericpolymers, polyvinyl chloride elastomeric polymers, polyurethaneelastomeric polymers, polyester elastomeric polymers, and polyamideelastomeric polymers.

In certain embodiments, the plasticized composition further comprises atleast one thermal stabilizer. In certain embodiments, the at least onethermal stabilizer comprises one or more compounds selected from epoxycompounds, metallic stabilizers, phosphites, nitrogen-containingstabilizers, polyols, hydrotalcites, zeolites, and dawsonites.

Exemplary epoxy thermal stabilizers include, but are not limited to,epoxidized oils such as soybean oil, lard oil, olive oil, linseed oil,peanut oil, castor oil, corn oil, tung oil, and cottonseed oil. Otherexemplary epoxy thermal stabilizers may include, but are not limited to,epichlorhydrin/bis-phenol A resins, butoxypropylene oxide, glycidylepoxystearate, epoxidized alpha-olefins, epoxidized glycidyl soyate,epoxidized butyl toluate, glycidol, vinyl cyclo-hexene dioxide, glycidylethers of resorcinol, hydroquinone, 1,5-dihydroxynaphthalene-,glycerine, pentaerythritol, and sorbitol, allyl glycidyl ether, butylglycidyl ether, cyclohexane oxide, 4-(2,3-epoxyproproxy)acetophenone,mesityl oxide epoxide, and 2-ethyl-3-propyl glycidamine.

Exemplary phosphite thermal stabilizers include, but are not limited to,trialkylphosphites such as trioctyl phosphite, tridecyl phosphite,tridodecyl phosphite, tri(tetradecyl) phosphite, tricyclohexylphosphite, tristearyl phosphite, distearyl-pentaerythritol diphosphite,and trioleyl phosphite; triaryl phosphites such as triphenyl phosphite,tricresyl phosphite, and tris-p-nonylphenyl phosphite, alkyldiarylphosphites such as phenyldidecyl phosphite and(2,4-di-tert-butylphenyl)didodecyl phosphite, dialkylaryl phosphites,and thiophosphites such as trithiohexyl phosphite, trithiooctylphosphite, trithiolauryl phosphite, and trithiobenzyl phosphite.

Exemplary metallic thermal stabilizers include, but are not limited to,metal salts and organometallic salts, such as oxides, hydroxides,sulfides, sulfates, halides, phosphates, phenates, perchlorates,carboxylates, and carbonates of metals like zinc, barium, strontium,calcium, tin, magnesium, cobalt, nickel, titanium, antimony, andaluminum, such as calcium hydroxide, magnesium hydroxide, calciumstearate, calcium 2-ethylhexanoate, calcium octanoate, calciumrecinoaleate, calcium myristate, calcium palmitate, barium laurate,barium di(nonylphenolate), barium stearate, aluminum stearate, andhydrotalcite. Exemplary organometallic thermal stabilizers also include,but are not limited to, organotin carboxylates and mercaptides, such asbutyltin tris dodecyl mercaptide, dibutylin dilaurate, dibutyltindidodecyl mercaptide, dianhydride tris dibutylstannane diol,dihydrocarbontin salts of carboxy mercaptals, monosulfides and/orpolysulfides of the organotin mercaptides of mercaptoalkyl carboxylatesand/or alkyl thioglycolates.

Exemplary nitrogen-containing thermal stabilizers include, but are notlimited to, dicyandiamide, hindered amines, melamine, urea, dimethylhydantoin, guanidine, thiourea, 2-phenylindoles, aminocrontonates,N-alkyl and N-phenyl substituted maleimides, 1,3-dialkyl-6-amino-uracilderivatives, pyrrolodiazine diones, and monomeric, oligomeric, andpolymeric 2,2,6,6-tetramethylpiperidine compounds. Other exemplarynonmetallic stabilizers include, but are not limited to,dilaurylthiodipropionate, distearyl 3,3′-thiopropionate,dibenzyl-3,3′-thiodipropionate, dicyclohexyl-3,3′-thiodipropionate,dioleyl-3,3′-thiodipropionate, didecyl-3,3′-thiodipropionate,diethyl-3,3′-thiodipropionate, lauryl ester of 3-mercaptopropionic acid,lauryl ester of 3-lauryl mercaptopropionic acid, and the phenyl ester of3-octyl mercaptopropionic acid.

In addition to the at least one epoxidized estolide compound, theplasticized compositions described herein may further comprise one ormore plasticizers selected from petroleum-derived phthalates andbenzoate compounds, such as dioctyl phthalate (DOP) and diallylphthalate (DAP). Other exemplary plasticizers include, but are notlimited to, one or more of the exemplary epoxy compound previouslydescribed herein. In certain embodiments, non-epoxidized estolidecompounds, such as those used to prepare the epoxidized estolidesdescribed herein, may also be used as plasticizers. Accordingly, incertain embodiments, the plasticized composition comprises at least onepolymeric material and co-blend of at least one epoxidized estolide andat least one non-epoxidized estolide.

In certain embodiments, the plasticized composition further comprises atleast one additive comprising one or more compounds selected fromdiluents, pigments, colorants, UV absorbers, fillers, and flameretarding agents. Exemplary diluents include, but are not limited to,hydrocarbons and ketones that are liquids at 25° C. Exemplaryhydrocarbons include aromatic, aliphatic, and/or cycloaliphatichydrocarbons.

In certain embodiments, the plasticized composition may be useful as afilm, coating, ink, or paint composition. In certain embodiments, theplasticized composition comprises a coating that may be applied ontometallic or non-metallic surfaces by dipping, spraying, or the use ofcoating rollers. In certain embodiments, the plasticized compositioncomprises a coating to be applied to fabrics, such as those used in theconstruction of resilient floor and wall coverings.

In certain embodiments, the plasticized composition comprises a solid,semi-solid, and/or molded material. In certain embodiments, theplasticized composition comprises an article of manufacture. In certainembodiments, the article of manufacture comprises one or more itemsselected from cookware, storage ware, furniture, appliances, automotivecomponents, boat components, toys, sportswear, medical devices, medicalimplants, containers, tubes, pipes, sporting equipment, electronics,wire jacketing, cable jacketing, crates, containers, packaging, labware,floor mats, instrumentation, liquid storage containers, bags, pouches,bottles, adhesives, shoe soles, gaskets, elastic fibers, and sealants.In certain embodiments the article is manufactured by any method knownto those of skill in the art. In certain embodiments, the method ofmanufacture is selected from injection molding, compression molding,transfer molding, casting, extruding, thermoforming, blow molding, androtational molding.

The present disclosure further relates to methods of making estolidesthat can be sulfurized and/or epoxidized to provide compounds accordingto Formula I, II, and III. By way of example, the reaction of anunsaturated fatty acid with an organic acid and the esterification ofthe resulting free acid estolide are illustrated and discussed in thefollowing Schemes 1 and 2. The particular structural formulas used toillustrate the reactions correspond to those for synthesis of compoundsthat can be subsequently sulfurized and/or epoxidized to providecompounds according to Formula I and III; however, the methods applyequally to the synthesis of compounds according to Formula II, with useof compounds having structure corresponding to R₃ and R₄ with a reactivesite of unsaturation.

As illustrated below, compound 100 represents an unsaturated fatty acidthat may serve as the basis for preparing the estolide compoundsdescribed herein.

In Scheme 1, wherein x is, independently for each occurrence, an integerselected from 0 to 20, y is, independently for each occurrence, aninteger selected from 0 to 20, n is an integer greater than or equal to1, and R₁ is an optionally substituted alkyl that is saturated orunsaturated, and branched or unbranched, unsaturated fatty acid 100 maybe combined with compound 102 and a proton from a proton source to formfree acid estolide 104. In certain embodiments, compound 102 is notincluded, and unsaturated fatty acid 100 may be exposed alone to acidicconditions to form free acid estolide 104, wherein R₁ would represent anunsaturated alkyl group. In certain embodiments, if compound 102 isincluded in the reaction, R₁ may represent one or more optionallysubstituted alkyl residues that are saturated or unsaturated andbranched or unbranched. Any suitable proton source may be implemented tocatalyze the formation of free acid estolide 104, including but notlimited to homogenous acids and/or strong acids like hydrochloric acid,sulfuric acid, perchloric acid, nitric acid, triflic acid, and the like.

Similarly, in Scheme 2, wherein x is, independently for each occurrence,an integer selected from 0 to 20, y is, independently for eachoccurrence, an integer selected from 0 to 20, n is an integer greaterthan or equal to 1, and R₁ and R₂ are each an optionally substitutedalkyl that is saturated or unsaturated, and branched or unbranched, freeacid estolide 104 may be esterified by any suitable procedure known tothose of skilled in the art, such as acid-catalyzed reduction withalcohol 202, to yield esterified estolide 204. Other exemplary methodsmay include other types of Fischer esterification, such as those usingLewis acid catalysts such as BF₃.

As discussed above, in certain embodiments, the estolides describedherein may have improved properties which render them useful inlubricating compositions. Such applications may include, withoutlimitation, crankcase oils, gearbox oils, hydraulic fluids, drillingfluids, two-cycle engine oils, greases, and the like. Other suitableuses may include marine applications, where biodegradability andtoxicity are of concern. In certain embodiments, the nontoxic nature ofcertain estolides described herein may also make them suitable for useas lubricants in the cosmetic and food industries.

In some embodiments, it may be desirable to prepare lubricantcompositions comprising one or more of the estolides described herein.For example, in certain embodiments, the estolides described herein maybe blended with one or more additives selected from polyalphaolefins,synthetic esters, polyalkylene glycols, mineral oils (Groups I, II, andIII), pour point depressants, viscosity modifiers, anti-corrosives,antiwear agents, detergents, dispersants, colorants, antifoaming agents,and demulsifiers. In addition, or in the alternative, in certainembodiments, the estolides described herein may be co-blended with oneor more synthetic or petroleum-based oils to achieve desired viscosityand/or pour point profiles. In certain embodiments, certain estolidesdescribed herein also mix well with gasoline, so that they may be usefulas fuel components or additives.

In all of the foregoing examples, the compounds described may be usefulalone, as mixtures, or in combination with other compounds,compositions, and/or materials.

Methods for obtaining the novel compounds described herein will beapparent to those of ordinary skill in the art, suitable proceduresbeing described, for example, in the examples below, and in thereferences cited herein.

EXAMPLES Analytics

Nuclear Magnetic Resonance: NMR spectra were collected using a BrukerAvance 500 spectrometer with an absolute frequency of 500.113 MHz at 300K using CDCl₃ as the solvent. Chemical shifts were reported as parts permillion from tetramethylsilane. The formation of a secondary ester linkbetween fatty acids, indicating the formation of estolide, was verifiedwith ¹H NMR by a peak at about 4.84 ppm.

Estolide Number (EN): The EN was measured by GC analysis. It should beunderstood that the EN of a composition specifically refers to ENcharacteristics of any estolide compounds present in the composition.Accordingly, an estolide composition having a particular EN may alsocomprise other components, such as natural or synthetic additives, othernon-estolide base oils, fatty acid esters, e.g., triglycerides, and/orfatty acids, but the EN as used herein, unless otherwise indicated,refers to the value for the estolide fraction of the estolidecomposition.

Iodine Value (IV): The iodine value is a measure of the degree of totalunsaturation of an oil. IV is expressed in terms of centigrams of iodineabsorbed per gram of oil sample. Therefore, the higher the iodine valueof an oil the higher the level of unsaturation is of that oil. The IVmay be measured and/or estimated by GC analysis. Where a compositionincludes unsaturated compounds other than estolides as set forth inFormula I, II, and III, the estolides can be separated from otherunsaturated compounds present in the composition prior to measuring theiodine value of the constituent estolides. For example, if a compositionincludes unsaturated fatty acids or triglycerides comprising unsaturatedfatty acids, these can be separated from the estolides present in thecomposition prior to measuring the iodine value for the one or moreestolides.

Acid Value: The acid value is a measure of the total acid present in anoil. Acid value may be determined by any suitable titration method knownto those of ordinary skill in the art. For example, acid values may bedetermined by the amount of KOH that is required to neutralize a givensample of oil, and thus may be expressed in terms of mg KOH/g of oil.

Gas Chromatography (GC): GC analysis was performed to evaluate theestolide number (EN) and iodine value (IV) of the estolides. Thisanalysis was performed using an Agilent 6890N series gas chromatographequipped with a flame-ionization detector and an autosampler/injectoralong with an SP-2380 30 m×0.25 mm i.d. column.

The parameters of the analysis were as follows: column flow at 1.0mL/min with a helium head pressure of 14.99 psi; split ratio of 50:1;programmed ramp of 120-135° C. at 20° C./min, 135-265° C. at 7° C./min,hold for 5 min at 265° C.; injector and detector temperatures set at250° C.

Measuring EN and IV by GC: To perform these analyses, the fatty acidcomponents of an estolide sample were reacted with MeOH to form fattyacid methyl esters by a method that left behind a hydroxy group at siteswhere estolide links were once present. Standards of fatty acid methylesters were first analyzed to establish elution times.

Sample Preparation: To prepare the samples, 10 mg of estolide wascombined with 0.5 mL of 0.5M KOH/MeOH in a vial and heated at 100° C.for 1 hour. This was followed by the addition of 1.5 mL of 1.0 MH₂SO₄/MeOH and heated at 100° C. for 15 minutes and then allowed to coolto room temperature. One (1) mL of H₂O and 1 mL of hexane were thenadded to the vial and the resulting liquid phases were mixed thoroughly.The layers were then allowed to phase separate for 1 minute. The bottomH₂O layer was removed and discarded. A small amount of drying agent(Na₂SO₄ anhydrous) was then added to the organic layer after which theorganic layer was then transferred to a 2 mL crimp cap vial andanalyzed.

EN Calculation: The EN is measured as the percent hydroxy fatty acidsdivided by the percent non-hydroxy fatty acids. As an example, a dimerestolide would result in half of the fatty acids containing a hydroxyfunctional group, with the other half lacking a hydroxyl functionalgroup. Therefore, the EN would be 50% hydroxy fatty acids divided by 50%non-hydroxy fatty acids, resulting in an EN value of 1 that correspondsto the single estolide link between the capping fatty acid and basefatty acid of the dimer.

IV Calculation: The iodine value is estimated by the following equationbased on ASTM Method D97 (ASTM International, Conshohocken, Pa.):

${I\; V} = {\sum\; {100 \times \frac{A_{f} \times M\; W_{I} \times d\; b}{M\; W_{f}}}}$

-   -   A_(f)=fraction of fatty compound in the sample    -   MW_(I)=253.81, atomic weight of two iodine atoms added to a        double bond    -   db=number of double bonds on the fatty compound    -   MW_(f)=molecular weight of the fatty compound

The properties of exemplary estolide compounds and compositionsdescribed herein are identified in the following examples and tables.

Other Measurements: Except as otherwise described, pour point ismeasured by ASTM Method D97-96a, cloud point is measured by ASTM MethodD2500, viscosity/kinematic viscosity is measured by ASTM Method D445-97,viscosity index is measured by ASTM Method D2270-93 (Reapproved 1998),specific gravity is measured by ASTM Method D4052, flash point ismeasured by ASTM Method D92, evaporative loss is measured by ASTM MethodD5800, vapor pressure is measured by ASTM Method D5191, and acuteaqueous toxicity is measured by Organization of Economic Cooperation andDevelopment (OECD) 203.

Example 1

The acid catalyst reaction was conducted in a 50 gallon PfaudlerRT-Series glass-lined reactor. Oleic acid (65 Kg, OL 700, Twin Rivers)was added to the reactor with 70% perchloric acid (992.3 mL, AldrichCat#244252) and heated to 60° C. in vacuo (10 torr abs) for 24 hrs whilecontinuously being agitated. After 24 hours the vacuum was released.2-Ethylhexanol (29.97 Kg) was then added to the reactor and the vacuumwas restored. The reaction was allowed to continue under the sameconditions (60° C., 10 torr abs) for 4 more hours. At which time, KOH(645.58 g) was dissolved in 90% ethanol/water (5000 mL, 90% EtOH byvolume) and added to the reactor to quench the acid. The solution wasthen allowed to cool for approximately 30 minutes. The contents of thereactor were then pumped through a 1 micron (μ) filter into anaccumulator to filter out the salts. Water was then added to theaccumulator to wash the oil. The two liquid phases were thoroughly mixedtogether for approximately 1 hour. The solution was then allowed tophase separate for approximately 30 minutes. The water layer was drainedand disposed of. The organic layer was again pumped through a 1μ filterback into the reactor. The reactor was heated to 60° C. in vacuo (10torr abs) until all ethanol and water ceased to distill from solution.The reactor was then heated to 100° C. in vacuo (10 torr abs) and thattemperature was maintained until the 2-ethylhexanol ceased to distillfrom solution. The remaining material was then distilled using a Myers15 Centrifugal Distillation still at 200° C. under an absolute pressureof approximately 12 microns (0.012 torr) to remove all monoestermaterial leaving behind estolides (Ex. 1). Certain data are reportedbelow in Tables 1 and 8.

Example 2

The acid catalyst reaction was conducted in a 50 gallon PfaudlerRT-Series glass-lined reactor. Oleic acid (50 Kg, OL 700, Twin Rivers)and whole cut coconut fatty acid (18.754 Kg, TRC 110, Twin Rivers) wereadded to the reactor with 70% perchloric acid (1145 mL, AldrichCat#244252) and heated to 60° C. in vacuo (10 torr abs) for 24 hrs whilecontinuously being agitated. After 24 hours the vacuum was released.2-Ethylhexanol (34.58 Kg) was then added to the reactor and the vacuumwas restored. The reaction was allowed to continue under the sameconditions (60° C., 10 torr abs) for 4 more hours. At which time, KOH(744.9 g) was dissolved in 90% ethanol/water (5000 mL, 90% EtOH byvolume) and added to the reactor to quench the acid. The solution wasthen allowed to cool for approximately 30 minutes. The contents of thereactor were then pumped through a 1μ filter into an accumulator tofilter out the salts. Water was then added to the accumulator to washthe oil. The two liquid phases were thoroughly mixed together forapproximately 1 hour. The solution was then allowed to phase separatefor approximately 30 minutes. The water layer was drained and disposedof. The organic layer was again pumped through a 1μ filter back into thereactor. The reactor was heated to 60° C. in vacuo (10 torr abs) untilall ethanol and water ceased to distill from solution. The reactor wasthen heated to 100° C. in vacuo (10 ton abs) and that temperature wasmaintained until the 2-ethylhexanol ceased to distill from solution. Theremaining material was then distilled using a Myers 15 CentrifugalDistillation still at 200° C. under an absolute pressure ofapproximately 12 microns (0.012 torr) to remove all monoester materialleaving behind estolides (Ex. 2). Certain data are reported below inTables 2 and 7.

Example 3

The estolides produced in Example 1 (Ex. 1) were subjected todistillation conditions in a Myers 15 Centrifugal Distillation still at300° C. under an absolute pressure of approximately 12 microns (0.012torr). This resulted in a primary distillate having a lower EN average(Ex. 3A), and a distillation residue having a higher EN average (Ex.3B). Certain data are reported below in Tables 1 and 8.

TABLE 1 Pour Iodine Estolide Point Value Base Stock EN (° C.) (cg/g) Ex.3A 1.35 −32 31.5 Ex. 1 2.34 −40 22.4 Ex. 3B 4.43 −40 13.8

Example 4

Estolides produced in Example 2 (Ex. 2) were subjected to distillationconditions in a Myers 15 Centrifugal Distillation still at 300° C. underan absolute pressure of approximately 12 microns (0.012 torr). Thisresulted in a primary distillate having a lower EN average (Ex. 4A), anda distillation residue having a higher EN average (Ex. 4B). Certain dataare reported below in Tables 2 and 7.

TABLE 2 Estolide Iodine Base Stock EN Pour Point (° C.) Value (cg/g) Ex.4A 1.31 −30 13.8 Ex. 2 1.82 −33 13.2 Ex. 4B 3.22 −36 9.0

Example 5

Estolides produced by the method set forth in Example 1 were subjectedto distillation conditions (ASTM D-6352) at 1 atm over the temperaturerange of about 0° C. to about 710° C., resulting in 10 differentestolide cuts recovered at increasing temperatures The amount ofmaterial distilled from the sample in each cut and the temperature atwhich each cut distilled (and recovered) are reported below in Table 3:

TABLE 3 Cut (% of total) Temp. (° C.) 1 (1%) 416.4 2 (1%) 418.1 3 (3%)420.7  4 (20%) 536.4  5 (25%) 553.6  6 (25%) 618.6  7 (20%) 665.7 8 (3%)687.6 9 (1%) 700.6 10 (1%)  709.1

Example 6

Estolides made according to the method of Example 2 were subjected todistillation conditions (ASTM D-6352) at 1 atm over the temperaturerange of about 0° C. to about 730° C., which resulted in 10 differentestolide cuts. The amount of each cut and the temperature at which eachcut was recovered are reported in Table 4.

TABLE 4 Cut (% of total) Temp. (° C.) 1 (1%) 417.7 2 (1%) 420.2 3 (3%)472.0 4 (5%) 509.7  5 (15%) 533.7  6 (25%) 583.4  7 (25%) 636.4 8 (5%)655.4 9 (5%) 727.0 10 (15%) >727.0

Example 7

Estolide base oil 4B (from Example 4) was subjected to distillationconditions (ASTM D-6352) at 1 atm over the temperature range of about 0°C. to about 730° C., which resulted in 9 different estolide cuts. Theamount of each cut and the temperature at which each cut was recoveredare reported in Table 5a.

TABLE 5A Cut (% of total) Temp. (° C.) 1 (1%) 432.3 2 (1%) 444.0 3 (3%)469.6 4 (5%) 521.4  5 (15%) 585.4  6 (25%) 617.1  7 (25%) 675.1 8 (5%)729.9  9 (20%) >729.9

Example 8

Estolides were made according to the method set forth in Example 1,except that the 2-ethylhexanol esterifying alcohol used in Example 1 wasreplaced with various other alcohols. Alcohols used for esterificationinclude those identified in Table 5b below. The properties of theresulting estolides are set forth in Table 9.

TABLE 5b Alcohol Structure Jarcol ™ I-18CG iso-octadecanol Jarcol ™ I-122-butyloctanol Jarcol ™ I-20 2-octyldodecanol Jarcol ™ I-162-hexyldecanol Jarcol ™ 85BJ cis-9-octadecen-l-ol Fineoxocol ® 180

Jarcol ™ I-18T 2-octyldecanol

Example 9

Estolides were made according to the method set forth in Example 2,except the 2-ethylhexanol esterifying alcohol was replaced withisobutanol. The properties of the resulting estolides are set forth inTable 9.

Example 10

Estolides of Formula I, II, and III are prepared according to the methodset forth in Examples 1 and 2, except that the 2-ethylhexanolesterifying alcohol is replaced with various other alcohols. Alcohols tobe used for esterifictaion include those identified in Table 6 below.Esterifying alcohols to be used, including those listed below, may besaturated or unsaturated, and branched or unbranched, or substitutedwith one or more alkyl groups selected from methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl,neopentyl, hexyl, isohexyl, and the like, to form a branched orunbranched residue at the R₂ position. Examples of combinations ofesterifying alcohols and R₂ Substituents are set forth below in Table 6:

TABLE 6 Alcohol R₂ Substituents C₁ alkanol methyl C₂ alkanol ethyl C₃alkanol n-propyl, isopropyl C₄ alkanol n-butyl, isobutyl, sec-butyl C₅alkanol n-pentyl, isopentyl neopentyl C₆ alkanol n-hexyl, 2-methylpentyl, 3- methyl pentyl, 2,2-dimethyl butyl, 2,3-dimethyl butyl C₇alkanol n-heptyl and other structural isomers C₈ alkanol n-octyl andother structural isomers C₉ alkanol n-nonyl and other structural isomersC₁₀ alkanol n-decanyl and other structural isomers C₁₁ alkanoln-undecanyl and other structural isomers C₁₂ alkanol n-dodecanyl andother structural isomers C₁₃ alkanol n-tridecanyl and other structuralisomers C₁₄ alkanol n-tetradecanyl and other structural isomers C₁₅alkanol n-pentadecanyl and other structural isomers C₁₆ alkanoln-hexadecanyl and other structural isomers C₁₇ alkanol n-heptadecanyland other structural isomers C₁₈ alkanol n-octadecanyl and otherstructural isomers C₁₉ alkanol n-nonadecanyl and other structuralisomers C₂₀ alkanol n-icosanyl and other structural isomers C₂₁ alkanoln-heneicosanyl and other structural isomers C₂₂ alkanol n-docosanyl andother structural isomers

TABLE 7 ASTM PROPERTY ADDITIVES METHOD Ex. 4A Ex. 2 Ex. 4B Color None —Light Amber Amber Gold Specific Gravity (15.5° C.), g/ml None D 40520.897 0.904 0.912 Viscosity - Kinematic at 40° C., cSt None D 445 32.565.4 137.3 Viscosity - Kinematic at 100° C., cSt None D 445 6.8 11.319.9 Viscosity Index None D 2270 175 167 167 Pour Point, ° C. None D 97−30 −33 −36 Cloud Point, ° C. None D 2500 −30 −32 −36 Flash Point, ° C.None D 92 n/a (>200) n/a (>250) n/a (>286) Fire Point, ° C. None D 92300 300 320 Evaporative Loss (NOACK), wt. % None D 5800 1.9 1.4 0.32Vapor Pressure - Reid (RVP), psi None D 5191 ≈0 ≈0 ≈0

TABLE 8 ASTM PROPERTY ADDITIVES METHOD Ex. 3A Ex. 1 Ex. 3B Color None —Light Gold Amber Amber Specific Gravity (15.5° C.), g/ml None D 40520.897 0.906 0.917 Viscosity - Kinematic at 40° C., cSt None D 445 40.991.2 211.6 Viscosity - Kinematic at 100° C., cSt None D 445 8.0 14.827.8 Viscosity Index None D 2270 172 170 169 Pour Point, ° C. None D 97−32 −40 −40 Cloud Point, ° C. None D 2500 −32 −33 −40 Flash Point, ° C.None D 92 278 286 306 Fire Point, ° C. None D 92 300 302 316 EvaporativeLoss (NOACK), wt. % None D 5800 1.4 0.8 0.3 Vapor Pressure - Reid (RVP),psi None D 5191 ≈0 ≈0 ≈0

TABLE 9 Ex- am- Estimated Pour Cloud Visc. Visc. ple EN Pt. Pt. @ @Visc. # Alcohol (approx.) ° C. ° C. 40° C. 100° C. Index 8 Jarcol™2.0-2.6 −15  −13 103.4 16.6 174 I-18CG 8 Jarcol™ I-12 2.0-2.6 −39  −40110.9 16.9 166 8 Jarcol™ I-20 2.0-2.6 −42 <−42 125.2 18.5 166 8 Jarcol™I-16 2.0-2.6 −51 <−51  79.7 13.2 168 8 Jarcol™ 85BJ 2.0-2.6 −15  −6123.8 19.5 179 8 Fineoxocol® 2.0-2.6 −39  −41 174.2 21.1 143 180 8Jarcol™ 2.0-2.6 −42 <−42 130.8 19.2 167 I-18T 8 Isobutanol 2.0-2.6 −36 −36  74.1 12.6 170 9 Isobutanol 1.5-2.2 −36  −36  59.5 10.6 170

Example 11

Saturated and unsaturated estolides having varying acid values weresubjected to several corrosion and deposit tests. These tests includedthe High Temperature Corrosion Bench Test (HTCBT) for several metals,the ASTM D130 corrosion test, and the MHT-4 TEOST (ASTM D7097) test forcorrelating piston deposits. The estolides tested having higher acidvalues (0.67 mg KOH/g) were produced using the method set forth inExamples 1 and 4 for producing Ex. 1 and Ex. 4A (Ex.1* and Ex.4A*below). The estolides tested having lower acid values (0.08 mg KOH/g)were produced using the method set forth in Examples 1 and 4 forproducing Ex. 1 and Ex. 4A except the crude free-acid estolide wasworked up and purified prior to esterification with BF₃.OET₂ (0.15equiv.; reacted with estolide and 2-EH in Dean Stark trap at 80° C. invacuo (10 torr abs) for 12 hrs while continuously being agitated; crudereaction product washed 4×H₂O; excess 2-EH removed by heating washedreaction product to 140° C. in vacuo (10 torr abs) for 1 hr) (Ex.4A#below). Estolides having an IV of 0 were hydrogenated via 10 wt. %palladium embedded on carbon at 75° C. for 3 hours under a pressurizedhydrogen atmosphere (200 psig) (Ex.4A*H and Ex.4A#H below) The corrosionand deposit tests were performed with a Dexos™ additive package. Resultswere compared against a mineral oil standard:

TABLE 10 Ex. 1* Ex. 4A* Ex. 4A*H Ex. 4A# Ex. 4A#H Standard EstolideEstolide Estolide Estolide Estolide Acid Value — ~0.7 0.67 0.67 0.080.08 (mg KOH/g) Iodine Value — ~45 16 0 16 0 (IV) HTCBT Cu 13 739 279 603.2 13.6 HTCBT Pd 177 11,639 1,115 804 4.93 243 HTCBT Sn 0 0 0 0 0 0ASTM D130 1A 4B 3A 1B 1A 1A MHT-4 18 61 70 48 12 9.3

Example 12

“Ready” and “ultimate” biodegradability of the estolide produced in Ex.1 was tested according to standard OECD procedures. Results of the OECDbiodegradability studies are set forth below in Table 11:

TABLE 11 301D 28-Day 302D Assay (% degraded) (% degraded) Canola Oil86.9 78.9 Ex. 1 64.0 70.9 Base Stock

Example 13

The Ex. 1 estolide base stock from Example 1 was tested under OECD 203for Acute Aquatic Toxicity. The tests showed that the estolides arenontoxic, as no deaths were reported for concentration ranges of 5,000mg/L and 50,000 mg/L.

Example 14

Estolides are made according to the method set forth in Example 1.50 gof the resulting estolides and elemental sulfur (1 g) are added to a 2liter, 4 neck flask fitted with a stirrer, thermowell, gas inlet tube,and Dean Stark trap with reflux condenser. The contents are heated to150° C. for 3 hours while sparging with nitrogen at 0.75 cubic feet perhour. The contents are permitted to cool to room temperature, and arefiltered to provide sulfurized estolides.

Example 15

Sulfurized estolides are made according to the method set forth inExample 14, except the sulfurization is performed separately on each ofthe estolides made according the methods set forth in Examples 2, 3 (3Aand 3B), and 4 (4A and 4B).

Example 16

Estolides were made according to the method set forth in Example 1, andprocessed according to the distillation conditions of Example 3 toprovide estolides of Ex. 3A and 3B. Ex. 3A estolides (1.0 eq.) wereadded to a round bottom flask, cooled to 5° C., along with aqueous H₂O₂(4 eq.) and formic acid (4.1 eq.). The mixture was stirred vigorouslyand allowed to warm to room temperature. Stirring of the reactionmixture was allowed to continue for a total of 72 hours. The reactionmixture was then extracted in a separatory funnel with hexanes andwashed with an aqueous sodium sulfite solution. The organic layer waswashed several more times with deionized water and dried over magnesiumsulfate (anhydrous), and filtered. The solvents were then removed in arotary evaporator to yield epoxidized estolides.

Example 17

Estolides were made according the method set forth in Example 1, exceptthe free-acid estolide intermediate was isolated prior to esterificationwith 2-EH. Instead, the water-washed free-acid estolide intermediate wasfiltered through a 1μ filter and isolated. The isolated free-acidestolide was then subjected to distillation conditions (Myers 15Centrifugal Distillation) to remove any unreacted fatty acid startingmaterials to provide a purified free-acid estolide product (Ex. 17FA).

Estolides of Example 17FA, Example 3 (3A, 3B), and Example 16(epoxidized Ex. 3A estolides) were separately blended with virgin PVCpowder (polyvinyl chloride homopolymer, OxyVinyls® 220F, OccidentalPetro. Corp.). The plasticized blends were transferred to an ExtrusionPlastometer (Tinius Olsen Model MP987). The blends were then heated to200° C., held for 5 minutes, and then extruded into strands forcharacterization. Results of the extrusion are set forth below in Table12:

TABLE 12 Plasticized Strand Blend No. Estolide (%) PVC % CharacteristicsPass/Fail 17A Ex. 17FA (15) 85 Non-continuous and Fail fragmented 17BEx. 3A (15) 85 Non-continuous and Fail fragmented 17C Ex. 3B (15) 85Non-continuous and Fail fragmented 17D Ex. 16 (epox. Ex. 85 Continuousand Pass 3A) (15) uniform

Example 18

Virgin PVC (OxyVinyls® 220F) and plasticized blend No. 17D of Example 17were subjected to Differential Scanning calorimetry (DSC) using aMettler DSC 820 with TSO 801RO Sample Robot to determine glasstransition temperature (Tg, ° C.). Results of the DSC testing are setforth below in Table 13:

TABLE 13 Sample Tg (° C.) Depression of Tg Virgin PVC 85 — Blend No. 17D64 25%

Example 19

Free-acid estolides are prepared according to the method set forth inExample 17 (Ex. 17FA). The free acid estolide product is furtherdistilled to provide a primary distillate having a lower EN (Ex. 19A)and a secondary distillate having a higher EN (Ex. 19B).

Example 20

Epoxidized estolides are made according to the method set forth inExample 16, except the estolides of Example 3A are replaced and theepoxidation is repeated separately on each of the estolides madeaccording the methods set forth in Example 1, Example 2, Example 3B,Example 4 (4A, 4B), Example 17 (Ex. 17FA), and Example 19 (19A, 19B).

Example 21

Plasticized blends are prepared and tested according to the method setforth in Example 17, except the estolides set forth therein are replacedwith those described in Example 20.

Example 22

Estolides were prepared according to the methods set forth in Example 17(Ex. 17FA), Example 3 (3A, 3B), and Example 16 (epoxidized Ex. 3A), andtested for stability using thermogravimetric analysis (TGA). The TGA wasperformed using a Mettler TGA 850 with TSO 801RO Sample Robot, in whicheach sample was initially heated from 30° C. to 165° C. at a rate of 20°C./min, and then held at 165° C. for 30 min. Results of the TGA testingare set forth below in Table 14, where % weight loss (from commencementof testing) is reported at separate time intervals:

TABLE 14 Ex. 8 min. 15 min. 25 min. 37 min. 17FA ~0.3% ~0.6% ~0.8% ~0.9% 3A <0.1% ~0.6% ~1.4% ~2.2%  3B   0%   0%   0%   0% 16 (epox. 3A) ~0.6%~1.1% ~1.4% ~1.6%

1. At least one compound of Formula I:

wherein W¹, W², W³, W⁴, W⁴, W⁶, and W⁷, independently for eachoccurrence, are selected from —CH₂—, —CH═CH—, —CHR₅—, and

provided that at least one of W¹, W², W³, W⁴, W⁵, W⁶, or W⁷ is —CHR₅— or

R₅ is selected from —S_(v)R₆, wherein v is an integer selected from 1 to8 and R₆ is selected from hydrogen and an estolide residue; T is S; z isan integer selected from 0 to 15; p is an integer selected from 0 to 15;q is an integer selected from 0 to 15; x is, independently for eachoccurrence, an integer selected from 0 to 20; y is, independently foreach occurrence, an integer selected from 0 to 20; n is equal to orgreater than 0; and R₂ is selected from hydrogen and optionallysubstituted alkyl that is saturated or unsaturated, and branched orunbranched, wherein each fatty acid chain residue of said at least onecompound is independently optionally substituted.
 2. The at least onecompound according to claim 1, wherein at least one of W¹, W², or W³ is—CHR₅— or


3. The at least one compound according to claim 1, wherein W³ is —CH₂—.4. The at least one compound according to claim 1, wherein W¹ is —CH₂—.5. The at least one compound according to claim 1, wherein W² isselected from —CHR₅— and


6. The at least one compound according to claim 5, wherein W² isselected from —CHR₅—, and R₅ is selected from —S_(v)R₆.
 7. The at leastone compound according to claim 1, wherein R₆ is an estolide residue. 8.The at least one compound according to claim 1, wherein v is an integerselected from 1 and
 2. 9. The at least one compound according to claim5, wherein W² is selected from

10-12. (canceled)
 13. The at least one compound according to claim 1,wherein z is an integer selected from 2 to
 8. 14. The at least onecompound according to claim 13, wherein z is
 6. 15. (canceled)
 16. Theat least one compound according to claim 1, wherein p is an integerselected from 1 to
 5. 17. (canceled)
 18. The at least one compoundaccording to claim 16, wherein p is
 1. 19. (canceled)
 20. The at leastone compound according to claim 1, wherein q is an integer selected from1 to
 8. 21. The at least one compound according to claim 1, wherein q isselected from 0 and
 1. 22. The at least one compound according to claim1, wherein q is an integer selected from 5 and
 6. 23. (canceled)
 24. Theat least one compound according to claim 1, wherein W² is selected from—CHR₅—, R₅ is selected from —S_(v)R₆, and p is an integer selected from1 and
 2. 25. The at least one compound according to claim 24, wherein v,independently for each occurrence, is an integer selected from 1 and 2.26. The at least one compound according to claim 1, wherein W² isselected from

and p is
 1. 27. The at least one compound according to claim 1, whereinthe compound is selected from at least one compound according to FormulaIII:


28. The at least one compound according to claim 1, wherein n is aninteger selected from 0 to
 12. 29. The at least one compound accordingto claim 28, wherein n is an integer selected from 0 to
 8. 30. The atleast one compound according to claim 29, wherein n is an integerselected from 0 to
 6. 31. The at least one compound according to claim1, wherein n is equal to or greater than
 1. 32. The at least onecompound according to claim 1, wherein x+y is, independently for eachchain, an integer selected from 13 to
 19. 33. The at least one compoundaccording to claim 32, wherein x+y is, independently for each chain, aninteger selected from 13 to
 15. 34. The at least one compound accordingto claim 1, wherein x+y is 15 for at least one chain.
 35. The at leastone compound according to claim 1, wherein R₂ is a branched orunbranched C₁ to C₂₀ alkyl that is saturated or unsaturated.
 36. The atleast one compound according to claim 1, wherein R₂ is selected frommethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decanyl, undecanyl, dodecanyl, tridecanyl, tetradecanyl, pentadecanyl,hexadecanyl, heptadecanyl, octadecanyl, nonadecanyl, and icosanyl, whichare saturated or unsaturated and branched or unbranched.
 37. The atleast one compound according to claim 35, wherein R₂ is selected from C₆to C₁₂ alkyl.
 38. The at least one compound according to claim 37,wherein R₂ is 2-ethylhexyl. 39-57. (canceled)
 58. The at least onecompound according to claim 1, wherein R₂ is hydrogen.
 59. The at leastone compound according to claim 1, wherein R₂ is an unsubstituted alkylthat is saturated or unsaturated, and branched or unbranched.
 60. The atleast one compound according to claim 27, wherein z is 6 and q is aninteger selected from 0 to 6.